Indeno-fused ring compounds

ABSTRACT

The present invention relates to compounds represented by the following Formulas (I) and (II), 
                         
Ring-A of Formulas I and II can be, for example, an aryl group, and Q′ and Q′″ can each be independently selected from groups, such as, halogen, —OH, —CN, amine groups, amide groups, carboxylic acid ester groups, carboxylic acid groups, alkenyl groups, alkynyl groups, carbonate groups, sulfide groups, and sulfonic acid ester groups. The present invention also relates to photochromic compositions and photochromic articles that include one or more photochromic compounds, such as represented by Formula II.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 12/928,687, filed Dec. 16, 2010, which is acontinuation-in-part of U.S. patent application Ser. No. 12/329,092,filed Dec. 5, 2008, which is a continuation-in-part of U.S. patentapplication Ser. No. 10/846,629, filed May 17, 2004 (now U.S. Pat. No.7,342,112), which is entitled to and claims the benefit of U.S.Provisional Application Ser. No. 60/484,100, filed Jul. 1, 2003, all ofwhich documents are hereby incorporated herein by reference in theirentireties.

FIELD OF THE INVENTION

The present invention relates to indeno-fused ring compounds, includingindeno-fused ring pyran compounds, which can be photochromic compounds,and compositions and articles that include the photochromic compounds ofthe present invention.

BACKGROUND OF THE INVENTION

Photochromic compounds typically have at least two states, a first statehaving a first absorption spectrum and a second state having a secondabsorption spectrum that differs from the first absorption spectrum, andare capable of switching between the two states in response to at leastactinic radiation. Further, conventional photochromic compounds can bethermally reversible. That is, photochromic compounds are capable ofswitching between a first state and a second state in response to atleast actinic radiation and reverting back to the first state inresponse to thermal energy. As used herein “actinic radiation” meanselectromagnetic radiation, such as but not limited to ultraviolet andvisible radiation that is capable of causing a response. Morespecifically, conventional photochromic compounds can undergo atransformation in response to actinic radiation from one isomer toanother, with each isomer having a characteristic absorption spectrum,and can further revert back to the first isomer in response to thermalenergy (i.e., be thermally reversible). For example, conventionalthermally reversible photochromic compounds are generally capable ofswitching from a first state, for example a “clear state,” to a secondstate, for example a “colored state,” in response to actinic radiationand reverting back to the “clear” state in response to thermal energy.

Dichroic compounds are compounds that are capable of absorbing one oftwo orthogonal plane polarized components of transmitted radiation morestrongly than the other. Thus, dichroic compounds are capable oflinearly polarizing transmitted radiation. As used herein, “linearlypolarize” means to confine the vibrations of the electric vector oflight waves to one direction or plane. However, although dichroicmaterials are capable of preferentially absorbing one of two orthogonalplane polarized components of transmitted radiation, if the molecules ofthe dichroic compound are not suitably positioned or arranged, no netlinear polarization of transmitted radiation will be achieved. That is,due to the random positioning of the molecules of the dichroic compound,selective absorption by the individual molecules will cancel each othersuch that no net or overall linear polarizing effect is achieved. Thus,it is generally necessary to suitably position or arrange the moleculesof the dichroic compound within another material in order to form aconventional linear polarizing element, such as a linearly polarizingfilter or lens for sunglasses.

In contrast to the dichroic compounds, it is generally not necessary toposition or arrange the molecules of conventional photochromic compoundsto form a conventional photochromic element. Thus, for example,conventional photochromic elements, such as lenses for photochromiceyewear, can be formed, for example, by spin coating a solutioncontaining a conventional photochromic compound and a “host” materialonto the surface of the lens, and suitably curing the resultant coatingor layer without arranging the photochromic compound in any particularorientation. Further, even if the molecules of the conventionalphotochromic compound were suitably positioned or arranged as discussedabove with respect to the dichroic compounds, because conventionalphotochromic compounds do not strongly demonstrate dichroism, elementsmade therefrom are generally not strongly linearly polarizing.

It would be desirable to develop new photochromic compounds that canexhibit useful photochromic and/or dichroic properties in at least onestate, and that can be used in a variety of applications to impartphotochromic and/or dichroic properties.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a compound,such as an indeno-fused ring compound, represented by the followingFormula I,

Ring-A of Formula I, and other related formulas disclosed furtherherein, is selected from, aside from the (R′)_(m)— group, unsubstitutedaryl, substituted aryl, unsubstituted fused ring aryl, substituted fusedring aryl, unsubstituted heteroaryl, and substituted heteroaryl. Withsome embodiments, Ring-A is selected from aryl, fused ring aryl, andheteroaryl.

The Q′ group of Formula-I, and other related formulas disclosed furtherherein, is selected from halogen, —OH, —N₃, —NR^(a)R^(a),—N(R^(a))C(O)Q″, —CN, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a),—C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a), —SR^(a),—OS(O₂)R^(b), —C(O)NR^(a)R^(a) and a lengthening agent L (as describedfurther herein). Each R^(a) is independently selected from hydrogen,hydrocarbyl and substituted hydrocarbyl each optionally andindependently interrupted with at least one of —O—, —S—, —C(O)—,—C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₁₄)_(u)(R₁₄)_(v)—, where u and v are each independently selectedfrom 0 to 2, provided that the sum of u and v is 2, and each R₁₄ isindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and combinations of two or more thereof. Alternatively, twoR^(a) groups can come together with —N and optionally an additionalhetero atom selected from N and O to form a heterocycloalkyl. The R^(b)group is selected from perhalohydrocarbyl, and Q″ is selected from halo,—OR^(a), —NR^(a)R^(a), —C(O)OR^(a), —SR^(a), and hydrocarbyl orsubstituted hydrocarbyl, wherein the substituents are selected from —OH,—NR^(a)R^(a), —C(O)OR^(a), —SR^(a).

Subscript i of Formula I is selected from 0 to 3. Subscript t of FormulaI is selected from 0 to a total number of positions to which R² can bebonded to Ring-A, such as from 0 to 10, or 0 to 7, or 0 to 5, or 0 to 4,or 0 to 3. Ring positions to which an R¹ group is not bonded, caninstead have hydrogen groups bonded thereto. Similarly, Ring-A positionsto which an R² group is not bonded, can instead have hydrogen groupsbonded thereto. With further reference to Formula I, R¹ for each i, andR² for each t, are each independently selected from, hydrocarbyl andsubstituted hydrocarbyl each optionally and independently interruptedwith at least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—, —S(O₂)—, —N═N—,—N(R₁₁′)— where R₁₁′ is selected from hydrogen, hydrocarbyl orsubstituted hydrocarbyl, —Si(OR₁₄)_(u)(R₁₄)_(v)—, where u and v are eachindependently selected from 0 to 2 (e.g., 0, 1 or 2), provided that thesum of u and v is 2, and each R₁₄ is independently selected fromhydrogen, hydrocarbyl and substituted hydrocarbyl, and combinations oftwo or more thereof; halogen; cyano; and —N(R₁₁′)R₁₂′, wherein R₁₁′ andR₁₂′ are each independently selected from hydrogen, hydrocarbyl orsubstituted hydrocarbyl, or R₁₁′ and R₁₂′ together form a ring structureoptionally including at least one heteroatom.

The R³ and R⁴ groups of Formula I are each independently selected from,hydrogen; hydrocarbyl and substituted hydrocarbyl each optionally andindependently interrupted with at least one of —O—, —S—, —C(O)—,—C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₁₄)_(u)(R₁₄)_(v)—, where u and v are each independently selectedfrom 0 to 2 (e.g., 0, 1 or 2), provided that the sum of u and v is 2,and each R₁₄ is independently selected from hydrogen, hydrocarbyl andsubstituted hydrocarbyl, and combinations of two or more thereof.Alternatively, R³ and R⁴ can together form a ring structure optionallyincluding at least one heteroatom.

The R⁵ group of Formula I is selected from hydrogen, —C(O)—R¹³ or—S(O₂)R¹³ wherein R¹³ is optionally substituted hydrocarbyl, oroptionally substituted halohydrocarbyl.

In accordance with the present invention, there is further provided acompound, such as an indeno-fused ring pyran compound, represented bythe following Formula II,

The various groups and subscripts of Formula II, such as R¹, R², R³, andR⁴, subscripts i and t, and Ring-A, are each as described previously andfurther herein with regard to the compound represented by Formula I. TheQ″′ group of Formula II, is selected from halogen, —OH, —N₃,—NR^(a)R^(a), —N(R^(a))C(O)Q″, —CN, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a),—C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a), —SR^(a),—OS(O₂)R^(b) and —C(O)NR^(a)R^(a). Each R^(a) group is independentlyselected from hydrogen, hydrocarbyl and substituted hydrocarbyl eachoptionally and independently interrupted with at least one of —O—, —S—,—C(O)—, —C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₁₄)_(u)(R₁₄)_(v)—, where u and v are each independently selectedfrom 0 to 2, provided that the sum of u and v is 2, and each R₁₄ isindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and combinations of two or more thereof, or two R^(a)groups come together with —N and optionally an additional hetero atomselected from N and O to form a heterocycloalkyl. The R^(b) group isselected from perhalohydrocarbyl, and Q″ is selected from halo, —OR^(a),—NR^(a)R^(a), —C(O)OR^(a), —SR^(a), and hydrocarbyl or substitutedhydrocarbyl, wherein the substituents are selected from —OH,—NR^(a)R^(a), —C(O)OR^(a), —SR^(a).

The B and B′ groups of Formula II are each independently selected fromhydrogen, unsubstituted aryl, substituted aryl, unsubstitutedheteroaryl, substituted heteroaryl, polyalkoxy, and polyalkoxy having apolymerizable group, or B and B′ taken together form a ring structureselected from unsubstituted fluoren-9-ylidene, substitutedfluoren-9-ylidene, saturated spiro-monocyclic hydrocarbon ring,saturated spiro-bicyclic hydrocarbon ring, and spiro-tricyclichydrocarbon ring.

In accordance with the present invention there is further providedphotochromic compositions and articles that include one or more of thecompounds of the present invention, such as compounds represented byFormula II.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphical representation of two average differenceabsorption spectrum obtained for a photochromic compound according tovarious non-limiting embodiments disclosed herein using the CELL METHOD.

DETAILED DESCRIPTION OF THE INVENTION

As used herein and in the claims, the term “actinic radiation” meanselectromagnetic radiation that is capable of transforming a photochromicmaterial from one form or state to another.

As used herein and in the claims, the term “photochromic” means havingan absorption spectrum for at least visible radiation that varies inresponse to absorption of at least actinic radiation. Further, as usedherein the term “photochromic material” means any substance that isadapted to display photochromic properties, i.e. adapted to have anabsorption spectrum for at least visible radiation that varies inresponse to absorption of at least actinic radiation, and which includesat least one photochromic compound.

As used herein and in the claims, the term “halo” and similar terms,such as halo group, halogen, and halogen group means F, Cl, Br and/or I,such as fluoro, chloro, bromo and/or iodo.

Unless otherwise indicated, all ranges or ratios disclosed herein are tobe understood to encompass any and all subranges or subratios subsumedtherein. For example, a stated range or ratio of “1 to 10” should beconsidered to include any and all subranges between (and inclusive of)the minimum value of 1 and the maximum value of 10; that is, allsubranges or subratios beginning with a minimum value of 1 or more andending with a maximum value of 10 or less, such as but not limited to, 1to 6.1, 3.5 to 7.8, and 5.5 to 10.

As used herein and in the claims, the articles “a,” “an,” and “the”include plural referents unless otherwise expressly and unequivocallylimited to one referent.

Other than in the operating examples, or where otherwise indicated, allnumbers expressing quantities of ingredients, reaction conditions, andso forth used in the specification and claims are to be under stood asmodified in all instances by the term “about.”

As used herein and in the claims, the term “precursor” and relatedterms, such as “precursors” with regard to the various groups, forexample, R¹, R², R³, R⁴, R⁵, Q′, Q″′, B, B′, and L, of the compounds andintermediates described herein, for example, the indeno-fused ringcompounds represented by Formula I, the indeno-fused ring pyrancompounds represented by Formula II, means a group that can be convertedin one or more steps to the final or desired group. For purposes ofnon-limiting illustration: a precursor of a hydroxyl group (—OH)includes, but is not limited to, a carboxylic acid ester group (—OC(O)Rwhere R is hydrogen or an optionally substituted hydrocarbyl); and aprecursor of a carboxylic acid ester group (—OC(O)R) includes, but isnot limited to, a hydroxyl group (—OH), which can be reacted, forexample, with a carboxylic acid halide, such as acetic acid chloride (oracetyl chloride).

Various groups of the compounds and intermediates described previouslyand further herein, such as but not limited to the R¹, R², R³, R⁴, R⁵,Q′, Q″′, B, B′, and lengthening agent L groups of the compoundsrepresented by Formulas I and II, and related formulas, can in each casebe independently selected from hydrocarbyl and substituted hydrocarbyl.

As used herein and in the claims the term “hydrocarbyl” and similarterms, such as “hydrocarbyl substituent” and “hydrocarbyl group” means:linear or branched C₁-C₂₀ alkyl (e.g., linear or branched C₁-C₁₀ alkyl);linear or branched C₂-C₂₀ alkenyl (e.g., linear or branched C₂-C₁₀alkenyl); linear or branched C₂-C₂₀ alkynyl (e.g., linear or branchedC₂-C₁₀ alkynyl); C₃-C₁₂ cycloalkyl (e.g., C₃-C₁₀ cycloalkyl); C₃-C₁₂heterocycloalkyl (having at least one hetero atom in the cyclic ring);C₅-C₁₈ aryl (including polycyclic aryl groups) (e.g., C₅-C₁₀ aryl);C₅-C₁₈ heteroaryl (having at least one hetero atom in the aromaticring); and C₆-C₂₄ aralkyl (e.g., C₆-C₁₀ aralkyl).

Representative alkyl groups include but are not limited to methyl,ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl,pentyl, neopentyl, hexyl, heptyl, octyl, nonyl and decyl. Representativealkenyl groups include but are not limited to vinyl, allyl and propenyl.Representative alkynyl groups include but are not limited to ethynyl,1-propynyl, 2-propynyl, 1-butynyl, and 2-butynyl. Representativecycloalkyl groups include but are not limited to cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl substituents.Representative heterocycloalkyl groups include but are not limited totetrahydrofuranyl, tetrahydropyranyl and piperidinyl. Representativearyl groups include but are not limited to phenyl and naphthyl.Representative heteroaryl groups include but are not limited to furanyl,pyranyl and pyridinyl. Representative aralkyl groups include but are notlimited to benzyl, and phenethyl.

The term “substituted hydrocarbyl” as used herein and in the claimsmeans a hydrocarbyl group in which at least one hydrogen thereof hasbeen substituted with a group that is other than hydrogen, such as, butnot limited to, halo groups, hydroxyl groups, ether groups, thiolgroups, thio ether groups, carboxylic acid groups, carboxylic acid estergroups, phosphoric acid groups, phosphoric acid ester groups, sulfonicacid groups, sulfonic acid ester groups, nitro groups, cyano groups,hydrocarbyl groups (e.g., alkyl, alkenyl, alkynyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, and aralkyl groups), and aminegroups, such as —N(R₁₁′)(R₁₂′) where R₁₁′ and R₁₂′ are eachindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, or R₁₁′ and R₁₂′ together form a cyclic ring optionallyincluding at least one heteroatom (e.g., —O—, —Si— and/or —S—).

The term “substituted hydrocarbyl” is inclusive of halohydrocarbyl (orhalo substituted hydrocarbyl) substituents. The term “halohydrocarbyl”as used herein and in the claims, and similar terms, such as halosubstituted hydrocarbyl, means that at least one hydrogen atom of thehydrocarbyl (e.g., of the alkyl, alkenyl, alkynyl, cycloalkyl,heterocycloalkyl, aryl, heteroaryl, and aralkyl groups) is replaced witha halogen atom selected from chlorine, bromine, fluorine and iodine. Thedegree of halogenation can range from at least one hydrogen atom beingreplaced by a halogen atom (e.g., a fluoromethyl group) to fullhalogenation (perhalogenation) in which all replaceable hydrogen atomson the hydrocarbyl group have been replaced by a halogen atom (e.g.,trifluoromethyl or perfluoromethyl). Correspondingly, the term“perhalohydrocarbyl group” as used herein and in the claims means ahydrocarbyl group in which all replaceable hydrogens have been replacedwith a halogen. Examples of perhalohydrocarbyl groups include, but arenot limited to, perhalogenated phenyl groups and perhalogenated alkylgroups.

The hydrocarbyl and substituted hydrocarbyl groups from which variousgroups and substituents, such as R¹, R², R³, R⁴, R⁵, Q′, Q″′ and L, caneach be selected, can in each case be independently and optionallyinterrupted with at least one of —O—, —S—, —C(O)—, —C(O)O—, —S(O)—,—S(O₂)—, —N═N—, —N(R₁₁′)—, and —Si(OR₁₄)_(u)(R₁₄)_(v)—. As used hereinand in the claims, by interrupted with at least one of —O—, —S—, —C(O)—,—C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)—, and —Si(OR₁₄)_(u)(R₁₄)_(v)—,means that at least one carbon of, but less than all of the carbons of,the hydrocarbyl group or substituted hydrocarbyl group, is in each caseindependently replaced with one of the recited divalent linking groups.The hydrocarbyl and substituted hydrocarbyl groups can be interruptedwith two or more of the above recited linking groups, which can beadjacent to each other or separated by one or more carbons.

As used herein and in the claims, unless otherwise indicated,left-to-right representations of linking groups, such as divalentlinking groups, are inclusive of other appropriate orientations, suchas, right-to-left orientations. For purposes of non-limitingillustration, the left-to-right representation of the divalent linkinggroup —C(O)O—, is inclusive of the right-to-left representation thereof,—O(O)C—.

As used herein and in the claims, recitations of “linear or branched” or“linear, branched or cyclic” groups, such as linear or branched alkyl,or linear, branched or cyclic alkyl, are herein understood to include: amethylene group or a methyl group; groups that are linear, such aslinear C₂-C₂₅ alkyl groups; groups that are appropriately branched, suchas branched C₃-C₂₅ alkyl groups; and groups that are appropriatelycyclic, such as C₃-C₂₅ cycloalkyl (or cyclic C₃-C₂₅ alkyl) groups.

With some embodiments of the present invention there is provided athermally reversible, photochromic compound having a Q′ or Q″′ group atthe position described previously and further herein, and optionally oneor more Lengthening groups L, as further described hereinafter. Othernon-limiting embodiments provide a photochromic compound adapted to haveat least a first state and a second state, in which the thermallyreversible, photochromic compound has an average absorption ratiogreater than 2.3 in at least one state as determined according to theCELL METHOD, which is described in detail below. Further, according tovarious non-limiting embodiments, the thermally reversible, photochromiccompound has an average absorption ratio greater than 2.3 in anactivated state as determined according to the CELL METHOD. As usedherein, the term “photochromic compound” (PC) refers to one or morephotochromic compounds, including, but not limited to the photochromiccompounds of the present invention, such as represented by Formula II.As used herein with respect to photochromic compounds, the term“activated state” refers to the photochromic compound when exposed tosufficient actinic radiation to cause the at least a portion of thephotochromic compound to switch states. Further, as used herein the term“compound” means a substance formed by the union of two or moreelements, components, ingredients, or parts and includes, withoutlimitation, molecules and macromolecules (for example polymers oroligomers) formed by the union of two or more elements, components,ingredients, or parts.

In general, the CELL METHOD of measuring average absorption ratio of aphotochromic compound involves obtaining an absorption spectrum for thephotochromic compound, in an activated or unactived state, in each oftwo orthogonal polarization directions while the photochromic compoundis at least partially aligned in an aligned liquid crystal medium thatis contained within a cell assembly. More specifically, the cellassembly comprises two opposing glass substrates that are spaced apartby 20 microns+/−1 micron. The substrates are sealed along two oppositeedges to form the cell. The inner surface of each of the glasssubstrates is coated with a polyimide coating, the surface of which hasbeen at least partially ordered by rubbing. Alignment of thephotochromic compound is achieved by introducing the photochromiccompound and a liquid crystal medium into the cell assembly and allowingthe liquid crystal medium to align with the rubbed polyimide surface.Because the photochromic compound is contained within the liquid crystalmedium, alignment of the liquid crystal medium causes the photochromiccompound to be aligned. It will be appreciated by those skilled in theart that the choice of the liquid crystal medium and the temperatureused during testing can affect the measured absorption ratio.Accordingly, as set forth in more detail in the Examples, for purposesof the CELL METHOD, absorption ratio measurements are taken at roomtemperature (73° F.+/−0.5° F. or better) and the liquid crystal mediumis Licristal® E7 (which is reported to be a mixture of cyanobiphenyl andcyanoterphenyl liquid crystal compounds).

Once the liquid crystal medium and the photochromic compound arealigned, the cell assembly is placed on an optical bench (which isdescribed in more detail in the Examples). To obtain the averageabsorption ratio in the activated state, activation of the photochromiccompound is achieved by exposing the photochromic compound to UVradiation for a time sufficient to reach a saturated or near saturatedstate (that is, a state wherein the absorption properties of thephotochromic compound do not substantially change over the interval oftime during which the measurements are made). Absorption measurementsare taken over a period of time (typically 10 to 300 seconds) at 3second intervals for light that is linearly polarized in a planeperpendicular to the optical bench (referred to as the 0° polarizationplane or direction) and light that is linearly polarized in a plane thatis parallel to the optical bench (referred to as the 90° polarizationplane or direction) in the following sequence: 0°, 90°, 90°, 0° etc. Theabsorbance of the linearly polarized light by the cell is measured ateach time interval for all of the wavelengths tested and the unactivatedabsorbance (i.e., the absorbance of the cell with the liquid crystalmaterial and the unactivated photochromic compound) over the same rangeof wavelengths is subtracted to obtain absorption spectra for thephotochromic compound in each of the 0° and 90° polarization planes toobtain an average difference absorption spectrum in each polarizationplane for the photochromic compound in the saturated or near-saturatedstate.

For purposes of non-limiting illustration and with reference to FIG. 1,there is shown the average difference absorption spectrum (generallyindicated 10) in one polarization plane that was obtained for aphotochromic compound according to one non-limiting embodiment disclosedherein. The average absorption spectrum (generally indicated 11) is theaverage difference absorption spectrum obtained for the samephotochromic compound in the orthogonal polarization plane.

Based on the average difference absorption spectra obtained for thephotochromic compound, the average absorption ratio for the photochromiccompound is obtained as follows. The absorption ratio of thephotochromic compound at each wavelength in a predetermined range ofwavelengths corresponding to λ_(max-vis)+/−5 nanometers (generallyindicated as 14 in FIG. 1), wherein λ_(max-vis) is the wavelength atwhich the photochromic compound had the highest average absorbance inany plane, is calculated according to the following equation:AR _(λi) =Ab ¹ _(λi) /Ab ² _(λi)  Eq. 1wherein, AR_(λi) is the absorption ratio at wavelength λi, Ab¹ _(λi) isthe average absorption at wavelength λi in the polarization direction(i.e., 0° or 90°) having the higher absorbance, and Ab² _(λi) is theaverage absorption at wavelength λi in the remaining polarizationdirection. As previously discussed, the “absorption ratio” refers to theratio of the absorbance of radiation linearly polarized in a first planeto the absorbance of the same wavelength radiation linearly polarized ina plane orthogonal to the first plane, wherein the first plane is takenas the plane with the highest absorbance.

The average absorption ratio (“AR”) for the photochromic compound isthen calculated by averaging the individual absorption ratios obtainedfor the wavelengths within the predetermined range of wavelengths (i.e.,λ_(max-vis)+/−5 nanometers) according to the following equation:AR=(λAR _(λi))/n _(i)  Eq. 2wherein, AR is average absorption ratio for the photochromic compound,AR_(λi) are the individual absorption ratios (as determined above inEq. 1) for each wavelength within the predetermined the range ofwavelengths (i.e., λ_(max-vis)+/−5 nanometers), and n_(i) is the numberof individual absorption ratios averaged.

As previously discussed, conventional thermally reversible photochromiccompounds are adapted to switch from a first state to a second state inresponse to actinic radiation, and to revert back to the first state inresponse to thermal energy. More specifically, conventional thermallyreversible, photochromic compounds are capable of transforming from oneisomeric form (for example and without limitation, a closed form) toanother isomeric form (for example and without limitation, an open form)in response to actinic radiation, and reverting back to the closed formwhen exposed to thermal energy. However, as previously discussed,generally conventional thermally reversible photochromic compounds donot strongly demonstrate dichroism.

As discussed above, non-limiting embodiments disclosed herein provide athermally reversible photochromic compound having an average absorptionratio greater than 1.5 in at least one state as determined according toCELL METHOD and/or a thermally reversible photochromic compound that canbe used as an intermediate in the preparation of a photochromic compoundhaving an absorption ratio greater than 1.5. Thus, the thermallyreversible photochromic compound according to this non-limitingembodiment can display useful photochromic properties and/or usefulphotochromic and dichroic properties. That is, the thermally reversible,photochromic compound can be a thermally reversible, photochromic and/orphotochromic-dichroic compound. As used herein with respect to thephotochromic compounds described herein, the term“photochromic-dichroic” means displaying both photochromic and dichroicproperties under certain conditions, which properties are at leastdetectable by instrumentation.

In accordance with other non-limiting embodiments, the thermallyreversible photochromic compounds can be thermally reversiblephotochromic-dichroic compounds having an average absorption ratioranging from 4 to 20, from 3 to 30, or from 2.0 to 50 in at least onestate as determined according to CELL METHOD. It will be appreciated bythose skilled in the art that the higher the average absorption ratio ofthe photochromic compound the more linearly polarizing the photochromiccompound will be. Therefore, according to various non-limitingembodiments, the thermally reversible photochromic compounds can haveany average absorption ratio required to achieve a desired level oflinear polarization.

Another non-limiting embodiment provides a thermally reversible,photochromic compound that is free of oxazines and adapted to have atleast a first state and a second state, wherein the photochromiccompound has an average absorption ratio of at least 1.5 in at least onestate as determined according to CELL METHOD. Further, according to thisnon-limiting embodiment, the average absorption ratio can range from 1.5to 50 in at least one state as determined according to CELL METHOD.

The groups and substituents of the compounds of the present invention,such as those represented by Formulas I and II, and related compounds aswill be described in further detail herein, and the compounds andintermediates used in their preparation, are described in further detailas follows.

Ring-A of the compounds of the present invention, such as the compoundsrepresented by Formula I and Formula II, can in each case beindependently selected from unsubstituted aryl, substituted aryl,unsubstituted fused ring aryl, substituted fused ring aryl,unsubstituted heteroaryl, and substituted heteroaryl. Typically, Ring-A,aside from the (R¹)_(i)— group, is selected from unsubstituted aryl,unsubstituted fused ring aryl, and unsubstituted heteroaryl (or aryl,fused ring aryl, and heteroaryl). Examples of aryl groups from whichRing-A can be selected include, but are not limited to, phenyl andbiphenyl. Examples of fused ring aryl groups from which Ring-A can beselected include, but are not limited to, polycyclic aromatichydrocarbons, such as naphthyl and anthracenyl. Examples of heteroarylgroups from which Ring-A can be selected include, but are not limitedto, furanyl, pyranyl and pyridinyl.

The Q′ and Q″′ groups of the compounds of the present invention can withsome embodiments each be independently selected from, halogen, —OH, —N₃,—CN, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)),—OC(O)R^(a), —OC(O)OR^(a), —SR^(a), —OS(O₂)R^(b) and —C(O)NR^(a)R^(a),in which each R^(a) is independently selected from hydrogen, hydrocarbyland substituted hydrocarbyl each optionally and independentlyinterrupted with divalent groups as described previously herein. Withsome embodiments, for Q′ and Q″′, each R^(a) group is independentlyselected from hydrogen, an unsubstituted or substituted alkyl grouphaving from 1 to 18 carbon atoms, an unsubstituted or substituted arylgroup, an unsubstituted or substituted alkene or alkyne group havingfrom 2 to 18 carbon atoms, wherein said substituents are chosen fromhalo and hydroxyl, and R^(b) is selected from a perfluorinated alkylgroup having from 1 to 18 carbon atoms. Examples of perfluorinated alkylgroups include, but are not limited to, perfluoromethyl (—CF₃),perfluoro ethyl (—CF₂CF₃), perfluoropropy, including perfluoro-n-propyl,perfluoro-iso-propyl, perfluorobutyl including isomers thereof, such asperfluoro-n-butyl and perfluoro-t-butyl, and perfluorooctyl, includingisomers thereof.

With some further embodiments of the present invention, for Q′ and Q″′,each R^(a) group is independently selected from hydrogen and an alkylgroup having from 1 to 6 carbon atoms, and R^(b) is selected from aperfluorinated alkyl group having from 1 to 6 carbon atoms.

The Q′ and Q″′ groups, with some embodiments, can each be independentlyselected from bromo, fluoro, chloro, —N₃, —NR^(a)R^(a), —N(R^(a))C(O)Q″,—C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)),—OC(O)R^(a), —OC(O)OR^(a), —SR^(a), —OS(O₂)R^(b), —C(O)NR^(a)R^(a). Q′can also be lengthening agent L (as described further herein). EachR^(a) group can be independently selected from hydrogen, anunsubstituted or substituted alkyl group having from 1 to 18 carbonatoms, an unsubstituted or substituted aryl group, an unsubstituted orsubstituted alkene or alkyne group having from 2 to 18 carbon atoms,wherein said substituents are chosen from halo and hydroxyl.Alternatively two R^(a) groups can come together with —N and anadditional hetero atom selected from N and O to form a heterocycloalkyl.The R^(b) group can be selected from a perfluorinated alkyl group havingfrom 1 to 18 carbon atoms. The Q″ group can be selected from —OR^(a),—NR^(a)R^(a), —C(O)OR^(a), —SR^(a), and hydrocarbyl or substitutedhydrocarbyl, wherein the substituents are selected from —OH,—NR^(a)R^(a), —C(O)OR^(a), —SR^(a).

With further embodiments, Q′ and Q′″ are each independently selectedfrom bromo, chloro, —NR^(a)R^(a), —C(O)R^(a), and —C(O)OR^(a). The Q′group can also be lengthening agent L. Each R^(a) is independentlyselected from hydrogen and an alkyl group having from 1 to 6 carbonatoms. Alternatively, two R^(a) groups come together with —N and anadditional N atom to form a heterocycloalkyl. The R^(b) group isselected from a perfluorinated alkyl group having from 1 to 6 carbonatoms.

With some embodiments of the present invention, Q′″ is not selected fromlengthening agent L.

The R⁵ group of the indeno-fused ring compounds of the presentinvention, such as those represented by Formula I above, and Formula Ia(as will be described further herein), can be selected from hydrogen,—C(O)—R¹³ or —S(O₂)R¹³, in which R¹³ is hydrocarbyl, or halohydrocarbyl.With some embodiments, R⁵ is selected from hydrogen and —C(O)—R¹³.Typically, R¹³ can be selected from C₁-C₁₂ or C₁-C₆ alkyl groups orperhaloalkyl groups, such as perfluoroalkyl groups.

For the indeno-fused ring compounds, such as represented by Formula I,and the indeno-fused ring pyran compounds, such as represented byFormula II, of the present invention, R¹ for each i, and R² for each t,are each independently selected from: (a) —C(O)X₂₄; (b) —OX₇ and—N(X₇)₂; (c) —SX₁₁; (d) a nitrogen containing ring represented byFormula i, as will be described in further detail herein; (e) a grouprepresented by Formula II and iii, as will be described in furtherdetail herein; (f) or immediately adjacent R¹ groups, and immediatelyadjacent R² groups, in each case independently together form a grouprepresented by Formula vii, viii, or ix, as will be described in furtherdetail herein; (g) a lengthening agent L represented by Formula III aswill be described in further detail herein; and (h) a group B, as willbe described in further detail herein.

With some embodiments, R¹ for each i, and R² for each t, are eachindependently selected from, (a) —C(O)X₂₄, in which X₂₄ is chosen from alengthening agent L (as will be described further herein), hydroxy,C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, phenyl that is unsubstituted ormono-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, amino that isunsubstituted, mono- or di-substituted with at least one of C₁-C₁₈alkyl, phenyl, benzyl, and naphthyl.

With some further embodiments, R¹ for each i, and R² for each t, areeach independently selected from, (a) —C(O)X₂₄, in which X₂₄ is chosenfrom a lengthening agent L (as will be described further herein),hydroxy, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, phenyl that is unsubstituted ormono-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy, amino that isunsubstituted, mono- or di-substituted with at least one of C₁-C₆ alkyl,phenyl, benzyl, and naphthyl.

In accordance with further embodiments, R¹ for each i, and R² for eacht, are each independently selected from, (a) —C(O)X₂₄, in which X₂₄ ischosen from hydroxy, C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl that isunsubstituted or mono-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy,amino that is unsubstituted, mono- or di-substituted with at least oneof C₁-C₆ alkyl, phenyl, benzyl, and naphthyl.

With some embodiments, R¹ for each i, and R² for each t, are eachindependently selected from, (b) —OX₇ and —N(X₇)₂, in which each X₇ isindependently chosen from four categories of groups (i), (ii), (iii),and (iv). With some embodiments, X₇ is chosen from, (i) hydrogen, alengthening agent L (as will be described further herein), C₁-C₁₈ alkyl,C₁-C₁₈ acyl, phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkyl substitutedphenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkoxy substituted phenyl(C₁-C₁₈)alkyl;C₁-C₁₆ alkoxy(C₁-C₁₈)alkyl; C₃-C₁₀ cycloalkyl; mono(C₁-C₁₈)alkylsubstituted C₃-C₁₀ cycloalkyl, C₁-C₁₈ haloalkyl, allyl, benzoyl,mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl,wherein each of said benzoyl and naphthoyl substituents areindependently chosen from C₁-C₁₈ alkyl, and C₁-C₁₈ alkoxy. Each X₇ canindependently be chosen from, (ii) —CH(X₈)X₉, wherein X₈ is chosen fromhydrogen, a lengthening agent L, or C₁-C₁₈ alkyl, and X₉ is chosen froma lengthening agent L, —CN, —CF₃, or —COOX₁₀, wherein X₁₀ is chosen fromhydrogen, a lengthening agent L (as will be described further herein),or C₁-C₁₈ alkyl. Each X₇ can independently be chosen from, (iii)—C(O)X₆, in which X₆ is chosen from at least one of, hydrogen, alengthening agent L (as will be described further herein), C₁-C₁₈alkoxy, phenoxy that is unsubstituted, mono- or di-substituted withC₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an aryl group that is unsubstituted,mono- or di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an aminogroup that is unsubstituted, mono- or di-substituted with C₁-C₁₈ alkyl,and a phenylamino group that is unsubstituted, mono- or di-substitutedwith C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy. In addition, each X₇ canindependently be chosen from, (iv) tri(C₁-C₁₈)alkylsilyl,tri(C₁-C₁₈)alkylsilyloxy, tri(C₁-C₁₈)alkoxysilyl,tri(C₁-C₁₈)alkoxysilyloxy, di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyl,di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyloxy, di(C₁-C₁₈)alkoxy(C₁-C₁₈alkyl)silyl or di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyloxy.

With further embodiments of the present invention, R¹ for each i, and R²for each t, are each independently selected from, (b) —OX₇ and —N(X₇)₂,in which each X₇ is independently chosen from, (i) hydrogen, alengthening agent L, C₁-C₁₂ alkyl, C₁-C₁₂ acyl, phenyl(C₁-C₁₂)alkyl,mono(C₁-C₁₂)alkyl substituted phenyl(C₁-C₁₂)alkyl, mono(C₁-C₁₂) alkoxysubstituted phenyl(C₁-C₁₂)alkyl; C₁-C₁₂ alkoxy(C₁-C₁₂)alkyl; C₃-C₇cycloalkyl; mono(C₁-C₁₂)alkyl substituted C₃-C₇ cycloalkyl, C₁-C₁₂haloalkyl, allyl, benzoyl, mono-substituted benzoyl, naphthoyl ormono-substituted naphthoyl, wherein each of said benzoyl and naphthoylsubstituents are independently chosen from C₁-C₆ alkyl, and C₁-C₆alkoxy. Each X₇ can also be independently selected from, (ii) —CH(X₈)X₉,wherein X₈ is chosen from hydrogen, a lengthening agent L, or C₁-C₁₂alkyl; and X₉ is chosen from a lengthening agent L, —CN, —CF₃, or—COOX₁₀, wherein X₁₀ is chosen from hydrogen, a lengthening agent L, orC₁-C₁₂ alkyl. Each X₇ can be further selected from, (iii) —C(O)X₈,wherein X₆ is chosen from at least one of, hydrogen, a lengthening agentL, C₁-C₁₂ alkoxy, phenoxy that is unsubstituted, mono- or di-substitutedwith C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy, an aryl group that is unsubstituted,mono- or di-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy, an amino groupthat is unsubstituted, mono- or di-substituted with C₁-C₆ alkyl, and aphenylamino group that is unsubstituted, mono- or di-substituted withC₁-C₆ alkyl or C₁-C₆ alkoxy.

With additional embodiments of the present invention, R¹ for each i, andR² for each t, are each independently selected from, (b) —OX₇ and—N(X₇)₂, in which each X₇ is independently chosen from, (i) hydrogen,C₁-C₆ alkyl, C₁-C₆ acyl, phenyl(C₁-C₆)alkyl, mono(C₁-C₈)alkylsubstituted phenyl(C₁-C₈)alkyl, mono(C₁-C₆)alkoxy substitutedphenyl(C₁-C₆)alkyl; C₁-C₆ alkoxy(C₁-C₈)alkyl; C₃₋₅ cycloalkyl;mono(C₁-C₆)alkyl substituted C₃₋₅ cycloalkyl, C₁-C₆ haloalkyl, allyl,benzoyl, mono-substituted benzoyl, naphthoyl or mono-substitutednaphthoyl, wherein each of said benzoyl and naphthoyl substituents areindependently chosen from C₁-C₃ alkyl, and C₁-C₃ alkoxy. Each X₇ canalso be selected from, (ii) —CH(X₈)X₉, wherein X₈ is chosen fromhydrogen or C₁-C₆ alkyl; and X₉ is chosen from —CN, —CF₃, or —COOX₁₀,wherein X₁₀ is chosen from hydrogen or C₁-C₆ alkyl. Each X₇ can also befurther selected from, (iii) —C(O)X₆, wherein X₆ is chosen fromhydrogen, C₁-C₁₂ alkoxy, phenoxy that is unsubstituted, mono- ordi-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy, an aryl group that isunsubstituted, mono- or di-substituted with C₁-C₃ alkyl or C₁-C₃ alkoxy,an amino group that is unsubstituted, mono- or di-substituted with C₁-C₃alkyl, and a phenylamino group that is unsubstituted, mono- ordi-substituted with C₁-C₃ alkyl or C₁-C₃ alkoxy.

With some embodiments, R¹ for each i, and R² for each t, are eachindependently selected from, (c) —SX₁₁, wherein X₁₁ is chosen fromhydrogen, a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl, an arylgroup that is unsubstituted, or mono- or di-substituted with C₁-C₁₈alkyl, C₁-C₁₈ alkoxy, or halogen. The X₁₁ group of —SX₁₁ can also beselected from C₁-C₆ alkyl, C₁-C₆ haloalkyl, an aryl group (such as aphenyl group) that is unsubstituted, or mono- or di-substituted withC₁-C₆ alkyl, C₁-C₆ alkoxy, or halogen, such as chloro, bromo or fluoro.

With some embodiments, R¹ for each i, and R² for each t, are eachindependently selected from, (d) a nitrogen containing ring representedby the following Formula i:

With reference to Formula i, each —Y— is independently chosen for eachoccurrence from —CH₂—, —CH(R₁₃′)—, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-,and —C(R₁₃′)(aryl)-, and Z is —Y—, —O—, —S—, —S(O)—, —SO₂—, —NH—,—N(R₁₃′)—, or —N(aryl)-, wherein each R₁₃′ is independently alengthening group L, or C₁-C₂₀ alkyl (e.g., C₁-C₁₂ alkyl or C₁-C₆alkyl), each aryl is independently phenyl or naphthyl, m is an integer1, 2 or 3, and p is an integer 0, 1, 2, or 3, provided that when p is 0,Z is —Y—.

With further embodiments, R¹ for each i, and R² for each t, are eachindependently selected from, (e) a group represented by the followingFormula ii or Formula iii,

With reference to Formulas ii and iii, X₁₄, X₁₅, and X₁₆ areindependently chosen for each occurrence from hydrogen, a lengtheningagent L, C₁-C₁₈ alkyl, phenyl or naphthyl, or X₁₄ and X₁₅ together forma ring of 5 to 8 carbon atoms, p is an integer chosen from 0, 1, or 2,and X₁₇ is independently chosen for each occurrence from a lengtheningagent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen.

In accordance with additional embodiments, R¹ for each i, and R² foreach t, are each independently selected from, a group represented by theFormula II or Formula iii, as shown above, in which X₁₄, X₁₅, and X₁₆are independently chosen for each occurrence from hydrogen, alengthening agent L, C₁-C₁₂ alkyl, phenyl or naphthyl, or X₁₄ and X₁₅together form a ring of 5 to 7 carbon atoms; p is an integer chosen from0, 1, or 2, and X₁₇ is independently chosen for each occurrence from alengthening agent L, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, or halogen.

In accordance with further embodiments, R¹ for each i, and R² for eacht, are each independently selected from, a group represented by theFormula II or Formula iii, as shown above, in which X₁₄, X₁₅, and X₁₆are independently chosen for each occurrence from hydrogen, C₁-C₆ alkyl,or phenyl or X₁₄ and X₁₅ together form a ring of 5 to 7 carbon atoms; pis an integer chosen from 0, 1, or 2, and X₁₇ is independently chosenfor each occurrence from C₁-C₆ alkyl, C₁-C₆ alkoxy, or halogen.

According to some embodiments, immediately adjacent R¹ groups, andimmediately adjacent R² groups, in each case independently together forma group represented by the following Formulas vii, viii, or ix,

With reference to Formulas vii and viii, W and W′ W and W′ areindependently chosen for each occurrence from —O—, —N(X₇)—, —C(X₁₄)—,and —C(X₁₇)—. With further reference to Formulas vii, viii, and ix, X₁₄and X₁₅ are independently chosen for each occurrence from hydrogen, alengthening agent L, C₁-C₁₈ alkyl, phenyl or naphthyl, or X₁₄ and X₁₅together form a ring of 5 to 8 carbon atoms; and X₁₇ is independentlychosen for each occurrence from a lengthening agent L, C₁-C₁₈ alkyl,C₁-C₁₈ alkoxy, or halogen. With reference to Formula ix, q is an integerchosen from 0, 1, 2, 3, and 4.

In the case of some embodiments of the present invention, the nitrogencontaining ring represented by Formula i, can be alternativelyrepresented by the following Formulas-(XI) and -(XII).

In the case of Formulas-(XI) and -(XII), R_(17′) is in each instanceindependently selected from hydrogen or alkyl, such as C₁-C₆ alkyl, oroptionally substituted aryl, such as optionally substituted phenyl, andcorrespondingly, the nitrogen containing ring is selected fromsubstituted or unsubstituted piperidenyl (e.g., Formula-XI), and/orsubstituted or unsubstituted morpholinyl (e.g., Formula-XII).

In accordance with further embodiments of the present invention,immediately adjacent R¹ groups, and immediately adjacent R² groups, ineach case independently together form a group represented by Formulasvii, viii, or ix, as shown above, in which W and W′ are independentlychosen for each occurrence from —O—, —N(X₇)—, —C(X₁₄)—, and —C(X₁₇)—.The X₁₄ and X₁₅ groups are each independently chosen for each occurrencefrom hydrogen, a lengthening agent L, C₁-C₁₂ alkyl, phenyl or naphthyl,or X₁₄ and X₁₅ together form a ring of 5 to 7 carbon atoms; and X₁₇ isindependently chosen for each occurrence from a lengthening agent L,C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, or halogen. In addition, q is an integerchosen from 0 to 3.

In accordance with additional further embodiments of the presentinvention, immediately adjacent R¹ groups, and immediately adjacent R²groups, in each case independently together form a group represented byFormulas vii, viii, or ix, as shown above, in which W and W′ areindependently chosen for each occurrence from —O—, —N(X₇)—, —C(X₁₄)—,and —C(X₁₇)—. The X₁₄ and X₁₅ groups are independently chosen for eachoccurrence from hydrogen, C₁-C₆ alkyl, phenyl or naphthyl, or X₁₄ andX₁₅ together form a ring of 5 to 7 carbon atoms; and X₁₇ isindependently chosen for each occurrence from C₁-C₆ alkyl, C₁-C₆ alkoxy,or halogen. In addition, q is an integer chosen from 0 to 3.

The various groups of the indeno-fused ring compounds and indeno-fusedring pyran compounds of the present invention, including, but notlimited to, R¹ for each i, R² for each t, Q′, and Q′″, can eachindependently include or be selected from, a lengthening agent Lrepresented by the following Formula III,—(S₁)_(c)-(Q₁-(S₂)_(d))_(d′)-(Q₂-(S₃)_(e))_(e′)-(Q₃-(S₄)_(f))_(f′)—S₅—P  III

As used herein and the claims the term “lengthening agent L” and similarterms, such as lengthening agent and lengthening group, means in eachcase, a group that is independently selected from a group represented byFormula III as shown above, and as described in further detail asfollows.

As used herein, the term “attached” means directly bonded to orindirectly bonded to through another group. Thus, for example, accordingto various non-limiting embodiments disclosed herein, L can be directlybonded to the compounds of the present invention as a substituent on thecompound, or L can be a substituent on another group (such as a grouprepresented by R¹) that is directly bonded to the compound (i.e., L isindirectly bonded to the compound). Although not limiting herein,according to various non-limiting embodiments, L can be attached to thecompound so as to extend or lengthen the compound in an activated statesuch that the absorption ratio of the extended compound (e.g., thephotochromic compound) is enhanced as compared to the compound in theabsence of a lengthening agent. Although not limiting herein, accordingto various non-limiting embodiments, the location of attachment of L onthe compound can be chosen such that L lengthens the compound in atleast one of a direction parallel to or a direction perpendicular to atheoretical transitional dipole moment of the activated form of thecompound. Regarding the position of L, it can be subsequently attachedto the compound at the location of the Q′ or Q″′ group. The compounds ofthe present invention can have at least one Q′ or Q″′ group at theposition(s) indicated, and optionally one or more L groups. As usedherein the term “theoretical transitional dipole moment” refers totransient dipolar polarization created by interaction of electromagneticradiation with the molecule. See, for example, IUPAC Compendium ofChemical Technology, 2^(nd) Ed., International Union of Pure and AppliedChemistry (1997).

With some embodiments, each Q₁, Q₂, and Q₃ of Formula III isindependently chosen for each occurrence from, a divalent group chosenfrom, an unsubstituted or a substituted aromatic group, an unsubstitutedor a substituted alicyclic group, an unsubstituted or a substitutedheterocyclic group, and mixtures thereof. The substituents the Q₁, Q₂,and Q₃ can be chosen from, a group represented by P, liquid crystalmesogens, halogen, poly(C₁-C₁₈ alkoxy), C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈alkylcarbonyl, C₁-C₁₈ alkoxycarbonyloxy, aryloxycarbonyloxy,perfluoro(C₁-C₁₈)alkoxy, perfluoro(C₁-C₁₈)alkoxycarbonyl,perfluoro(C₁-C₁₈)alkylcarbonyl, perfluoro(C₁-C₁₈)alkylamino,di-(perfluoro(C₁-C₁₈)alkyl)amino, perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈alkylthio, C₁-C₁₈ acetyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkoxy, astraight-chain or branched C₁-C₁₈ alkyl group that is mono-substitutedwith cyano, halo, or C₁-C₁₈ alkoxy, or poly-substituted with halo, and agroup comprising one of the following formulae: -M(T)_((t-1)) and-M(OT)_((t-1)), wherein M is chosen from aluminum, antimony, tantalum,titanium, zirconium and silicon, T is chosen from organofunctionalradicals, organofunctional hydrocarbon radicals, aliphatic hydrocarbonradicals and aromatic hydrocarbon radicals, and t is the valence of M.

The subscripts c, d, e, and f of Formula-III are each independently aninteger selected from 0 to 20, inclusive of the recited values. The S₁,S₂, S₃, S₄, and S₅ groups of Formula-III are each independently for eachoccurrence a spacer unit chosen from the following categories (1), (2)and (3). The spacer units of category (1) include, optionallysubstituted alkylene, optionally substituted haloalkylene,—Si(Z′)₂(CH₂)_(g)—, and

wherein each Z′ is independently selected from hydrogen, C₁-C₁₈ alkyl,C₃-C₁₀ cycloalkyl, and aryl; g for each occurrence is independentlychosen from an integer from 1 to 20; h for each occurrence isindependently chosen from an integer from 1 to 16; and said substituentsfor the alkylene and haloalkylene are independently selected from C₁-C₁₈alkyl, C₃-C₁₀ cycloalkyl and aryl. The spacer units of category (2)include, —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—, —C(Z′)₂—C(Z′)₂— or a singlebond, wherein Z is independently chosen for each occurrence fromhydrogen, C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl and aryl, and Z′ isindependently chosen for each occurrence from C₁-C₁₈ alkyl, C₃-C₁₀cycloalkyl and aryl. The spacer units of category (3) include, —O—,—C(O)—, —C≡C—, —N═N—, —S—, —S(O)—, —S(O)(O)—, —(O)S(O)—, —(O)S(O)O—,—O(O)S(O)O—, or straight-chain or branched C₁-C₂₄ alkylene residue, saidC₁-C₂₄ alkylene residue being unsubstituted, mono-substituted by cyanoor halo, or poly-substituted by halo. With regard to the spacer unitsfrom which S₁, S₂, S₃, S₄, and S₅ can be chosen, there is the provisothat when two spacer units comprising heteroatoms are linked togetherthe spacer units are linked so that heteroatoms are not directly linkedto each other. With regard to the spacer units from which S₁, S₂, S₃,S₄, and S₅ can be chosen, there is the further proviso that when S₁ islinked to a compound of the present invention, such as Formula I, and S₅is linked to P, S₁ and S₅ are in each case so linked such that twoheteroatoms are not directly linked to each other.

With further reference to Formula-III, P is chosen from: hydroxy, amino,C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, azido, silyl, siloxy, silylhydride,(tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato, thioisocyanato,acryloyloxy, methacryloyloxy, 2-(acryloyloxy)ethylcarbamyl,2-(methacryloyloxy)ethylcarbamyl, aziridinyl, allyloxycarbonyloxy,epoxy, carboxylic acid, carboxylic ester, acryloylamino,methacryloylamino, aminocarbonyl, C₁-C₁₈ alkyl aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkyl, C₁-C₁₈ alkyloxycarbonyloxy, halocarbonyl,hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,amino(C₁-C₁₈)alkyl, C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino, C₁-C₁₈alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro,poly(C₁-C₁₈)alkyl ether, (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl,polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl,acryloyloxy(C₁-C₁₈)alkyl, methacryloyl, methacryloyloxy(C₁-C₁₈)alkyl,2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl,2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl,glycidyl, cyano, isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinylether, vinyl ester, a styrene derivative, main-chain and side-chainliquid crystal polymers, siloxane derivatives, ethyleneiminederivatives, maleic acid derivatives, fumaric acid derivatives,unsubstituted cinnamic acid derivatives, cinnamic acid derivatives thatare substituted with at least one of methyl, methoxy, cyano and halogen,or substituted or unsubstituted chiral or non-chiral monovalent ordivalent groups chosen from steroid radicals, terpenoid radicals,alkaloid radicals and mixtures thereof, wherein the substituents areindependently chosen from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano,cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is astructure having from 2 to 4 reactive groups, or P is an unsubstitutedor substituted ring opening metathesis polymerization precursor, or P isa substituted or unsubstituted photochromic compound.

The subscripts d′, e′ and f′ of Formula-III can each independentlychosen from 0, 1, 2, 3, and 4, provided that the sum of d′+e′+f′ is atleast 1 in some embodiments, or at least 2 in some further embodiments,or at least 3 in some additional embodiments.

According to various non-limiting embodiments disclosed herein, when Pis a polymerizable group, the polymerizable group can be any functionalgroup adapted to participate in a polymerization reaction. Non-limitingexamples of polymerization reactions include those described in thedefinition of “polymerization” in Hawley's Condensed Chemical DictionaryThirteenth Edition, 1997, John Wiley & Sons, pages 901-902, whichdisclosure is incorporated herein by reference. For example, althoughnot limiting herein, polymerization reactions include: “additionpolymerization,” in which free radicals are the initiating agents thatreact with the double bond of a monomer by adding to it on one side atthe same time producing a new free electron on the other side;“condensation polymerization,” in which two reacting molecules combineto form a larger molecule with elimination of a small molecule, such asa water molecule; and “oxidative coupling polymerization.” Further,non-limiting examples of polymerizable groups include hydroxy, acryloxy,methacryloxy, 2-(acryloxy)ethylcarbamyl, 2-(methacryloxy)ethylcarbamyl,isocyanate, aziridine, allylcarbonate, and epoxy, e.g., oxiranylmethyl.

According to further non-limiting embodiments, P can be chosen from amain-chain or a side-chain liquid crystal polymer and a liquid crystalmesogen. As used herein, the term liquid crystal “mesogen” means rigidrod-like or disc-like liquid crystal molecules. Further, as used hereinthe term “main-chain liquid crystal polymer” refers to a polymer havingliquid crystal mesogens within the backbone (i.e., the main chain)structure of the polymer. As used herein the term “side-chain liquidcrystal polymer” refers to a polymer having liquid crystal mesogensattached to the polymer at the side chains. Although not limitingherein, generally, the mesogens are made up of two or more aromaticrings that restrict the movement of a liquid crystal polymer. Examplesof suitable rod-like liquid crystal mesogens include without limitation:substituted or unsubstituted aromatic esters, substituted orunsubstituted linear aromatic compounds, and substituted orunsubstituted terphenyls.

According to another non-limiting embodiment, P can be chosen from asteroid radical, for example and without limitation, a cholesteroliccompound.

With some embodiments of the present invention, R¹ for each i, and R²for each t, are each independently selected from a group B. With someembodiments, the group B can be selected from (i) hydrogen, C₁-C₁₈alkyl, C₂-C₁₈ alkylidene, C₂-C₁₈ alkylidyne, vinyl, C₃-C₁₀ cycloalkyl,C₁-C₁₈ haloalkyl, allyl, halogen, and benzyl that is unsubstituted ormono-substituted with at least one of C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy.With further embodiments, the group B can be selected from (i) C₁-C₁₂alkyl, C₃-C₇ cycloalkyl, C₁-C₁₂ haloalkyl and benzyl that isunsubstituted or mono-substituted with at least one of C₁-C₆ alkyl andC₁-C₆ alkoxy. With still further embodiments, the group B can beselected from (i) C₁-C₆ alkyl, C₃-C₅ cycloalkyl, C₁-C₆ haloalkyl andbenzyl that is unsubstituted or mono-substituted with at least one ofC₁-C₃ alkyl and C₁-C₃ alkoxy.

In accordance with embodiments of the present invention, the group B canbe selected from (ii) phenyl that is mono-substituted at the paraposition with at least one substituent chosen from: C₁-C₁₈ alkoxy,linear or branched chain C₁-C₂₀ alkylene, linear or branched chain C₁-C₄polyoxyalkylene, cyclic C₃-C₂₀ alkylene, phenylene, naphthylene, C₁-C₁₈alkyl substituted phenylene, mono- or poly-urethane(C₁-C₂₀)alkylene,mono- or poly-ester(C₁-C₂₀)alkylene, mono- orpoly-carbonate(C₁-C₂₀)alkylene, polysilanylene, polysiloxanylene andmixtures thereof, wherein the at least one substituent is connected toan aryl group of a photochromic material.

With some further embodiments, group B can be selected from (iii)—CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from at least one ofhydrogen, a lengthening agent L, C₁-C₁₈ alkyl that is unsubstituted ormono-substituted with phenyl, phenyl(C₁-C₁₈)alkyl that ismono-substituted with C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl or C₁-C₁₈ alkoxy,and an aryl group that is unsubstituted, mono- or di-substituted,wherein each aryl substituent is independently chosen from C₁-C₁₈ alkyland C₁-C₁₈ alkoxy, and lengthening agent L. With some additionalembodiments, the group B can be selected from —CH(CN)₂ and —CH(COOX₁)₂,wherein X₁ is chosen from at least one of hydrogen, a lengthening agentL, C₁-C₁₂ alkyl that is unsubstituted or mono-substituted with phenyl,phenyl(C₁-C₆)alkyl that is mono-substituted with C₁-C₆ alkyl or C₁-C₆alkoxy, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₆ alkyl and C₁-C₆ alkoxy; and lengthening agent L. With furtheradditional embodiments, group B can be selected from —CH(CN)₂ and—CH(COOX₁)₂, wherein X₁ is chosen from hydrogen, C₁-C₆ alkyl that isunsubstituted or mono-substituted with phenyl, phenyl(C₁-C₃)alkyl thatis mono-substituted with C₁-C₃ alkyl or C₁-C₃ alkoxy, and an aryl groupthat is unsubstituted, mono- or di-substituted, wherein each arylsubstituent is independently chosen from C₁-C₃ alkyl and C₁-C₃ alkoxy;and lengthening agent L.

With some embodiments, group B can be selected from (iv) —CH(X₂)(X₃).The X₂ group can be chosen from at least one of hydrogen, a lengtheningagent L, C₁-C₁₈ alkyl, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy. The X₃ group can be chosen from atleast one of —COOX₁, —COX₄, and —CH₂OX₅, wherein, X₄ is chosen from atleast one of morpholino, piperidino, amino that is unsubstituted, mono-or di-substituted with C₁-C₁₈ alkyl, and an unsubstituted, mono- ordi-substituted group chosen from phenylamino and diphenylamino, whereineach substituent is independently chosen from C₁-C₁₈ alkyl or C₁-C₁₈alkoxy; and X₅ is chosen from hydrogen, a lengthening agent L, —C(O)X₂,C₁-C₁₈ alkyl that is unsubstituted or mono-substituted with(C₁-C₁₈)alkoxy or phenyl, phenyl(C₁-C₁₈)alkyl that is mono-substitutedwith (C₁-C₁₈)alkoxy, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy.

With some further embodiments, group B can be selected from —CH(X₂)(X₃).The X₂ group can be chosen from at least one of a lengthening agent L,C₁-C₁₂ alkyl, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₈ alkyl and C₁-C₆ alkoxy. The X₃ group can be chosen from atleast one of —COOX₁, —COX₁, —COX₄, and —CH₂OX₅, wherein: X₄ is chosenfrom at least one of morpholino, piperidino, amino that isunsubstituted, mono- or di-substituted with C₁-C₆ alkyl, and anunsubstituted, mono or di-substituted group chosen from phenylamino anddiphenylamino, wherein each substituent is independently chosen fromC₁-C₆ alkyl or C₁-C₆ alkoxy; and X₅ is chosen from hydrogen, alengthening agent L, —C(O)X₂, C₁-C₁₂ alkyl that is unsubstituted ormono-substituted with (C₁-C₁₂)alkoxy or phenyl, phenyl(C₁-C₁₂)alkyl thatis mono-substituted with (C₁-C₁₂)alkoxy, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₆ alkyl and C₁-C₆ alkoxy.

With some further additional embodiments, group B can be selected from—CH(X₂)(X₃). The X₂ group can be chosen from at least one of alengthening agent L, C₁-C₈ alkyl, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₃ alkyl and C₁-C₃ alkoxy. The X₃ is chosenfrom at least one of —COOX₁, —COX₄, and —CH₂OX₅, wherein: X₄ group canbe chosen from at least one of morpholino, piperidino, amino that isunsubstituted, mono- or di-substituted with C₁-C₃ alkyl, and anunsubstituted, mono or di-substituted group chosen from phenylamino anddiphenylamino, wherein each substituent is independently chosen fromC₁-C₃ alkyl or C₁-C₃ alkoxy; and X₅ is chosen from hydrogen, alengthening agent L, —C(O)X₂, C₁-C₆ alkyl that is unsubstituted ormono-substituted with (C₁-C₆)alkoxy or phenyl, phenyl(C₁-C₁₂)alkyl thatis mono-substituted with (C₁-C₆)alkoxy, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₃ alkyl and C₁-C₃ alkoxy.

Group B can in some embodiments be selected from (v) an unsubstituted,mono-, di-, or tri-substituted aryl group; 9-julolidinyl; or anunsubstituted, mono- or di-substituted heteroaromatic group chosen frompyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazoyl, benzopyridyl, indolinyl, or fluorenyl. Each aryl andheteroaromatic group substituent can independently be chosen for eachoccurrence from: (1) a lengthening agent L; (2) —COOX₁ or —C(O)X₆; (3)aryl, halogen, haloaryl, C₃-C₁₀ cycloalkylaryl, and an aryl group thatis mono- or di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; (4)C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkyloxy(C₁-C₁₈)alkyl,aryl(C₁-C₁₈)alkyl, aryloxy(C₁-C₁₈)alkyl, mono- ordi-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkyl, mono- ordi-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkyl, C₁-C₁₈ haloalkyl, andmono(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl; (5) C₁-C₁₈ alkoxy, C₃-C₁₀ cycloalkoxy,cycloalkyloxy(C₁-C₁₈)alkoxy, aryl(C₁-C₁₈)alkoxy, aryloxy(C₁-C₁₈)alkoxy,mono- or di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkoxy, and mono- ordi-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkoxy; (6) aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkylene, amino, mono- or di-alkylamino,diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino,aziridino, indolino, piperidino, morpholino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy,acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂; (8) —SX₁₁; (9)a nitrogen containing ring represented by Formula i; (10) a grouprepresented by Formula II or iii; and (11) an unsubstituted ormono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl,imidazolinyl, pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl, oracridinyl, wherein each substituent is independently chosen from alengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, phenyl, hydroxy, aminoor halogen.

Each aryl and heteroaromatic group substituent can additionally andindependently be chosen for each occurrence from, (12) a grouprepresented by Formula iv or Formula v,

With reference to Formulas iv and v: (I) V′ is independently chosen ineach formula from —O—, —CH—, C₁-C₈ alkylene, and C₃-C₁₀ cycloalkylene;(II) V is independently chosen in each formula from —O— or —N(X₂₁)—,wherein X₂₁ is hydrogen, a lengthening agent L, C₁-C₁₈ alkyl, and C₂-C₁₈acyl, provided that if V is —N(X₂₁)—, V′ is —CH₂—; (III) X₁₈ and X₁₉ areeach independently chosen from hydrogen, a lengthening agent L, andC₁-C₁₈ alkyl; and (IV) k is chosen from 0, 1, and 2, and each X₂₀ isindependently chosen for each occurrence from a lengthening agent L,C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, hydroxy and halogen.

Each aryl and heteroaromatic group substituent can additionally andindependently be chosen for each occurrence from, (13) a grouprepresented by Formula vi,

With reference to Formula vi: (I) X₂₂ is chosen from hydrogen, alengthening agent L, and C₁-C₁₈ alkyl; and (II) X₂₃ is chosen from alengthening agent L and an unsubstituted, mono-, or di-substituted groupchosen from naphthyl, phenyl, furanyl and thienyl, wherein eachsubstituent is independently chosen for each occurrence from C₁-C₁₈alkyl, C₁-C₁₈ alkoxy, and halogen.

In accordance with some further embodiments, group B can be selectedfrom an unsubstituted, mono-, di-, or tri-substituted aryl group;9-julolidinyl; or an unsubstituted, mono- or di-substitutedheteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl,benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, orfluorenyl. Each aryl and heteroaromatic group substituent isindependently chosen for each occurrence from: (1) a lengthening agentL; (2) —COOX₁ or —C(O)X₈; (3) aryl, haloaryl, C₃-C₇ cycloalkylaryl, andan aryl group that is mono- or di-substituted with C₁-C₁₂ alkyl orC₁-C₁₂ alkoxy; (4) C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₃-C₇cycloalkyloxy(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkyl, aryloxy(C₁-C₁₂)alkyl,mono- or di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- ordi-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, haloalkyl, andmono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl; (5) C₁-C₁₂ alkoxy, C₃-C₇ cycloalkoxy,cycloalkyloxy(C₁-C₁₂)alkoxy, aryl(C₁-C₁₂)alkoxy, aryloxy(C₁-C₁₂)alkoxy,mono- or di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, and mono- ordi-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy; (6) amido, amino, mono- ordi-alkylamino, diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino,N-arylpiperazino, aziridino, indolino, piperidino, morpholino,thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,hydroxy, acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂; (8)an unsubstituted or mono-substituted group chosen from pyrazolyl,imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl,phenoxazinyl, phenazinyl, or acridinyl, wherein each substituent isindependently chosen from a lengthening agent L, C₁-C₆ alkyl, C₁-C₆alkoxy, phenyl, hydroxy, amino or halogen.

In accordance with some further embodiments, group B can be selectedfrom an unsubstituted, mono-, di-, or tri-substituted aryl group;9-julolidinyl; or an unsubstituted, mono- or di-substitutedheteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl,benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, orfluorenyl.

Each substituent can be independently chosen for each occurrence from:(1) a lengthening agent L; (2) —C(O)X₆; (3) aryl, haloaryl, C₃-C₇cycloalkylaryl, and an aryl group that is mono- or di-substituted withC₁-C₁₂ alkyl or C₁-C₁₂ alkoxy; (4) C₁-C₆ alkyl, C₃-C₅ cycloalkyl, C₃-C₅cycloalkyloxy(C₁-C₆)alkyl, aryl(C₁-C₆)alkyl, aryloxy(C₁-C₆)alkyl, mono-or di-(C₁-C₆)alkylaryl(C₁-C₆)alkyl, mono- ordi-(C₁-C₆)alkoxyaryl(C₁-C₆)alkyl, haloalkyl, andmono(C₁-C₆)alkoxy(C₁-C₆)alkyl; (5) C₁-C₆ alkoxy, C₃-C₆ cycloalkoxy,cycloalkyloxy(C₁-C₆)alkoxy, aryl(C₁-C₆)alkoxy, aryloxy(C₁-C₆)alkoxy,mono- or di-(C₁-C₆)alkylaryl(C₁-C₆)alkoxy, and mono- ordi-(C₁-C₆)alkoxyaryl(C₁-C₆)alkoxy; (6) aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkylene, amino, mono- or di-alkylamino,diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino,aziridino, indolino, piperidino, morpholino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy,acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂; and (8) anunsubstituted or mono-substituted group chosen from pyrazolyl,imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl,phenoxazinyl, phenazinyl, or acridinyl, wherein each substituent isindependently chosen from a lengthening agent L, C₁-C₃ alkyl, C₁-C₃alkoxy, phenyl, hydroxy, amino or halogen.

The R³ and R⁴ groups of the indeno-fused ring compounds, for examplerepresented by Formula I, and the indeno-fused ring pyran compounds, forexample represented by Formula II, of the present invention can each beindependently selected from: (i) hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀haloalkyl, C₃-C₁₀ cycloalkyl, allyl, benzyl, or mono-substituted benzyl,said benzyl substituents being chosen from halogen, C₁-C₂₀ alkyl orC₁-C₂₀ alkoxy; (ii) an unsubstituted, mono- di- or tri-substituted groupchosen from phenyl, naphthyl, phenanthryl, pyrenyl, quinolyl,isoquinolyl, benzofuranyl, thienyl, benzothienyl, dibenzofuranyl,dibenzothienyl, carbazolyl, or indolyl, said group substituents in eachcase being independently chosen from halogen, C₁-C₂₀ alkyl or C₁-C₂₀alkoxy; (iii) mono-substituted phenyl, said substituent located at thepara position being —(CH₂)_(t)— or —O—(CH₂)_(t)—, wherein t is theinteger 1, 2, 3, 4, 5 or 6, said substituent being connected to an arylgroup which is a member of a photochromic material; (iv) the group—CH(R¹⁰)G, wherein R¹⁰ is hydrogen, C₁-C₂₀ alkyl or the unsubstituted,mono- or di-substituted aryl groups phenyl or naphthyl, and G is—CH₂OR¹¹, wherein R¹¹ is hydrogen, —C(O)R¹⁰, C₁-C₂₀ alkyl, C₁-C₂₀alkoxy(C₁-C₂₀)alkyl, phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkoxy substitutedphenyl(C₁-C₂₀)alkyl, or the unsubstituted, mono- or di-substituted arylgroups phenyl or naphthyl, each of said phenyl and naphthyl groupsubstituents being C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy.

According to some alternative embodiments, (v) R³ and R⁴ can togetherform a spiro substituent selected from a substituted or unsubstitutedspiro-carbocyclic ring containing 3 to 6 carbon atoms, a substituted orunsubstituted spiro-heterocyclic ring containing 1 or 2 oxygen atoms and3 to 6 carbon atoms including the spirocarbon atom. Thespiro-carbocyclic ring and the spiro-heterocyclic ring are eachannellated with 0, 1 or 2 benzene rings. The substituents of the spirorings can be chosen from hydrogen or C₁-C₂₀ alkyl (e.g., C₁-C₆ alkyl).

In accordance with further embodiments of the present invention, R³ andR⁴ are each independently selected from hydrogen, C₁-C₈ alkyl, C₁-C₈haloalkyl, and C₃-C₇ cycloalkyl. Alternatively, R³ and R⁴ together canform a spiro substituent selected from a substituted or unsubstitutedspiro-carbocyclic ring containing 3 to 6 carbon atoms.

The B and B′ groups of the indeno-fused ring pyran compounds of thepresent invention, for example represented by Formula II, can eachindependently be selected from those classes, groups and examples asdescribed previously herein with regard to group B.

Alternatively, B and B′ can with some embodiments together formfluoren-9-ylidene, mono- or di-substituted fluoren-9-ylidene, or asaturated C₃-C₁₂ spiro-monocyclic hydrocarbon ring, saturated C₇-C₁₂spiro-bicyclic hydrocarbon rings, saturated C₇-C₁₂ spiro-tricyclichydrocarbon rings; and said fluoren-9-ylidene substituents beingselected from the group consisting of C₁-C₄ alkyl, C₁-C₄ alkoxy, bromo,fluoro and chloro.

Further alternatively, B and B′ can with some embodiments together formfluoren-9-ylidene, mono- or di-substituted fluoren-9-ylidene, or asaturated C₃-C₈ spiro-monocyclic hydrocarbon ring, saturated C₇-C₁₀spiro-bicyclic hydrocarbon rings, saturated C₇-C₁₀ spiro-tricyclichydrocarbon rings, said fluoren-9-ylidene substituents being selectedfrom the group consisting of C₁-C₃ alkyl, C₁-C₃ alkoxy, fluoro andchloro.

With some embodiments, B and B′ together form fluoren-9-ylidene,adamantylidene, bornylidene, norbornylidene orbicyclo(3.3.1)nonan-9-ylidene.

The indeno-fused ring compound can with some embodiments of the presentinvention, be represented by the following Formula Ia,

With reference to Formula Ia, subscript (t) is selected from 0 to 4, andthe groups R¹, R², R³, R⁴, R⁵, and Q′, and subscript (i) are each asdescribed previously herein.

With further embodiments, Q′ of the indeno-fused ring compoundrepresented by Formula Ia is selected from —CN, —C(O)OR^(a), —C(O)R^(a),—C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a),—SR^(a), —OS(O₂)R^(b) and —C(O)NR^(a)R^(a), in which R^(a) and R^(b) areeach independently as described previously herein.

In accordance with some embodiments of the present invention, theindeno-fused ring pyran compound is represented by the following FormulaIIa,

With reference to Formula IIa, subscript (t) is selected from 0 to 4,and the groups R¹, R², R³, R⁴, Q″′, B and B′, and subscript (i) are eachas described previously herein. The numbers within the ring structuresof Formula IIa indicate positions to which various groups can be bondedthereto. For example, B and B′ are each bonded to Position-3, R³ and R⁴are each bonded to Position-13, and Q″′ is bonded to Position-10. The R¹group(s) can be bonded to Positions-9, 11, and 12, and the R² group(s)can be bonded to Positions-5, 6, 7, and 8.

With further embodiments, Position-12 of the indeno-fused ring pyrancompound represented by Formula IIa, is substituted with hydrogen, andQ′″ is —CN.

With additional embodiments, and with further reference to theindeno-fused ring pyran compound represented by Formula IIa, i is atleast 1, Position-12 has R¹ bonded thereto, and Q′″ is selected from—N₃, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)),—OC(O)R^(a), —OC(O)OR^(a), —SR^(a), and —OS(O₂)R^(b).

In accordance with further embodiments of the present invention, eachlengthening agent L of the indeno-fused ring compounds and theindeno-fused ring pyran compounds of the present invention, can beindependently selected from the compounds listed in Table 1 of U.S. Pat.No. 7,342,112, which disclosure is incorporated herein by reference, andthe following compounds.

(4-((1s,4r)-4-pentylcyclohexyl)benzamido)phenyl

4-((4-((1s,4r)-4-pentylcyclohexyl)phenoxy)carbonyl)phenyl

4-(4-(4-((1s,4r)-4-pentylcyclohexyl)phenyl)benzamido) phenyl

4-((((1′s,4′r)-4′-pentyl-[1,1′-bi(cyclohexan)]-4-yl)oxy)carbonyl)phenyl

4-(4′-(4-pentylcyclohexyl)-[1,1′-biphenyl]-4-ylcarboxamido)phenyl

4-((4′-(4-pentylcyclohexyl)-[1,1′-biphenyl]-4-carbonyl)oxy)benzamido

4-(4′-(4-pentylcyclohexyl)-[1,1′-biphenyl]-4-carbonyl)piperazin-1-yl

4-(4-(4-((1s,4r)-4-pentylcyclohexyl)phenyl)benzamido)-2-(trifluoromethyl)phenyl

2-methyl-4-((1r,4r)-4-((4′-((1s,4r)-4-pentylcyclohexyl)biphenyl-4-yloxy)carbonyl)cyclohexanecarboxamido)phenyl

4′-((1r,1′s,4R,4′R)-4′-pentylbi(cyclohexane-4-)carbonyloxy)biphenylcarbonyloxy

4-(((3S,8S,9S,10R,13R,14S,17R)-10,13-dimethyl-17-((R)-6-methylheptan-2-yl)-2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-1H-cyclopenta[a]phenanthren-3-yloxy)carbonyl)piperazin-1-yl

4-((S)-2-methylbutoxy)phenyl)-10-(4-(((3R,3aS,6S,6aS)-6-(4′-((1s,4S)-4-pentylcyclohexyl)biphenylcarbonyloxy)hexahydrofuro[3,2-b]furan-3-yloxy)carbonyl)phenyl

The indeno-fused ring pyran compounds of the present invention, such asthose represented by Formulas II and IIa, can be used to rendercompositions and/or articles photochromic. Examples of articles that canbe rendered photochromic by the indeno-fused ring pyran compounds of thepresent invention include, but are not limited to, optical elements,displays, windows (or transparencies), mirrors, and components orelements of liquid crystal cells. As used herein the term “optical”means pertaining to or associated with light and/or vision. Examples ofoptical elements that can be rendered photochromic include, withoutlimitation, ophthalmic elements, display elements, windows, mirrors, andliquid crystal cell elements. As used herein the term “ophthalmic” meanspertaining to or associated with the eye and vision. Non-limitingexamples of ophthalmic elements include corrective and non-correctivelenses, including single vision or multi-vision lenses, which can beeither segmented or non-segmented multi-vision lenses (such as, but notlimited to, bifocal lenses, trifocal lenses and progressive lenses), aswell as other elements used to correct, protect, or enhance(cosmetically or otherwise) vision, including without limitation,magnifying lenses, protective lenses, visors, goggles, as well as,lenses for optical instruments (for example, cameras and telescopes). Asused herein the term “display” means the visible or machine-readablerepresentation of information in words, numbers, symbols, designs ordrawings. Non-limiting examples of display elements include screens,monitors, and security elements, such as security marks. As used hereinthe term “window” means an aperture adapted to permit the transmissionof radiation there-through. Non-limiting examples of windows includeautomotive and aircraft transparencies, windshields, filters, shutters,and optical switches. As used herein the term “mirror” means a surfacethat specularly reflects a large fraction of incident light. As usedherein the term “liquid crystal cell” refers to a structure containing aliquid crystal material that is capable of being ordered. Onenon-limiting example of a liquid crystal cell element is a liquidcrystal display.

Articles can be rendered photochromic with the indeno-fused ring pyrancompounds of the present invention by methods including, but not limitedto, imbibition methods, cast-in-place methods, coating methods, in-moldcoating methods, over-mold methods, and lamination methods. Withimbibition methods, the indeno-fused ring pyran compound is typicallydiffused into a polymeric material of a previously formed or fabricatedarticle, such as a substrate or previously applied coating or film.Imbibition can be performed by immersing the polymeric material of apreviously formed or fabricated article in a solution containing theindeno-fused ring pyran compound, with or without heating. Thereafter,although not required, the indeno-fused ring pyran compound can bebonded with the polymeric material (e.g., of the substrate or coating).

With cast-in-place methods, the indeno-fused ring pyran compound can bemixed with: a polymer and/or oligomer composition in solution or meltform; or monomer composition in liquid form, so as to form a castablephotochromic composition. The castable photochromic composition is thentypically introduced into the cavity of a mold (e.g., a lens mold). Thecastable photochromic composition is then set (e.g., cured) within themold so as to form a photochromic article.

With articles that include a substrate, the indeno-fused ring pyrancompounds of the present invention can be connected to at least aportion of the substrate as part of a coating that is connected to atleast a portion of the substrate. The substrate can be a polymericsubstrate or an inorganic substrate (such as, but not limited to, aglass substrate). The indeno-fused ring pyran compound of the presentinvention can be incorporated into at least a portion of a coatingcomposition prior to application of the coating composition to thesubstrate. Alternatively, a coating composition can be applied to thesubstrate, at least partially set, and thereafter the indeno-fused ringpyran compound of the present invention can be imbibed into at least aportion of the coating. As used herein, the terms “set” and “setting”include, without limitation, curing, polymerizing, cross-linking,cooling, and drying.

Photochromic articles can be prepared using the indeno-fused ring pyrancompounds of the present invention by art-recognized in-mold coating (orin-mold casting) methods. With in-mold coating methods, a photochromiccoating composition including the indeno-fused ring pyran compound ofthe present invention, which can be a liquid coating composition or apowder coating composition, is applied to at least a portion of theinterior surface of a mold, and then at least partially set. Thereafter,a polymer solution or melt, or oligomeric or monomeric solution ormixture is cast or molded within the mold cavity and in contact with thepreviously applied photochromic coating composition, and at leastpartially set. The resulting photochromic article is then removed fromthe mold. Non-limiting examples of powder coatings in which theindeno-fused ring pyran compounds according to various non-limitingembodiments disclosed herein can be employed are set forth in U.S. Pat.No. 6,068,797 at col. 7, line 50 to col. 19, line 42, which disclosureis hereby specifically incorporated by reference herein.

Photochromic articles prepared using the indeno-fused ring pyrancompounds of the present invention can also be formed by art-recognizedover-mold methods. Over-mold methods typically involve forming asubstrate within a mold, and then forming an interior space between thesubstrate and an interior surface of the mold, into which a photochromiccoating composition is then subsequently introduced (e.g., injected) andthen set (e.g., cured). Alternatively, over-mold methods can involveintroducing a previously formed substrate into a mold, such that aninterior space is defined between the substrate and an interior moldsurface, and thereafter a photochromic coating composition is introduced(e.g., injected) into the interior space.

Photochromic articles, prepared using the indeno-fused ring pyrancompounds of the present invention, can also be formed by art-recognizedlamination methods. With lamination methods, a film comprising theindeno-fused ring pyran compounds of the present invention can beadhered or otherwise connect to a portion of the substrate, with orwithout an adhesive and/or the application of heat and pressure.Thereafter, if desired, a second substrate can be applied over the firstsubstrate and the two substrates can be laminated together (e.g., by theapplication of heat and pressure) to form an element wherein the filmcomprising the indeno-fused ring pyran compound is interposed betweenthe two substrates. Methods of forming films comprising a photochromicmaterial can include for example and without limitation, combining aphotochromic material with a polymeric solution or oligomeric solutionor mixture, casting or extruding a film therefrom, and, if required, atleast partially setting the film. Additionally or alternatively, a filmcan be formed (with or without a photochromic material) and imbibed withthe photochromic material.

The indeno-fused ring pyran compounds of the present invention, can beused alone or in combination with other photochromic materials. Classesof photochromic materials that can be used in combination (e.g., inmixture) with the indeno-fused ring pyran compounds of the presentinvention include, but are not limited to: spiro(indoline)naphthoxazinesand spiro(indoline)benzoxazines, for example as described in U.S. Pat.Nos. 3,562,172, 3,578,602, 4,215,010, 4,342,668, 5,405,958, 4,637,698,4,931,219, 4,816,584, 4,880,667, and 4,818,096; benzopyrans, for exampleas described in U.S. Pat. Nos. 3,567,605, 4,826,977, 5,066,818,4,826,977, 5,066,818, 5,466,398, 5,384,077, 5,238,931, and 5,274,132;photochromic organo-metal dithizonates, such as, (arylazo)-thioformicarylhydrazidates, e.g., mercury dithizonates which are described in, forexample, U.S. Pat. No. 3,361,706; and fulgides and fulgimides, e.g., the3-furyl and 3-thienyl fulgides and fulgimides which are described inU.S. Pat. No. 4,931,220 at column 20, line 5 through column 21, line 38.

The present invention also relates to a photochromic composition thatincludes: (a) a indeno-fused ring pyran compound of the presentinvention; and (b) an organic material selected from a polymer, anoligomer, a monomer, and combinations of two or more thereof. Thepolymer of the photochromic composition can be selected frompolycarbonate, polyamide, polyimide, poly(meth)acrylate, polycyclicalkene, polyurethane, poly(urea)urethane, polythiourethane,polythio(urea)urethane, polyol(allyl carbonate), cellulose acetate,cellulose diacetate, cellulose triacetate, cellulose acetate propionate,cellulose acetate butyrate, polyalkene, polyalkylene-vinyl acetate,poly(vinylacetate), poly(vinyl alcohol), poly(vinyl chloride),poly(vinylformal), poly(vinylacetal), poly(vinylidene chloride),poly(ethylene terephthalate), polyester, polysulfone, polyolefin,copolymers thereof, and combinations thereof.

The photochromic compositions of the present invention can optionallyfurther include, at least one additive selected from dyes, alignmentpromoters, photoinitiators, thermal initiators, polymerizationinhibitors, solvents, light stabilizers, heat stabilizers, mold releaseagents, rheology control agents, leveling agents, free radicalscavengers, and adhesion promoters.

The present invention also relates to a photochromic coating compositionthat includes: (a) a indeno-fused ring pyran compound of the presentinvention; (b) a film forming composition selected from a curable resincomposition, a thermoplastic resin composition, and combinationsthereof; and (c) optionally a solvent composition.

The present invention also relates to photochromic articles that includethe indeno-fused ring pyran compound of the present invention. Examplesof photochromic articles of the preset invention include, but are notlimited to, optical elements selected from at least one of, anophthalmic element, a display element, a window, a mirror, packagingmaterial, an active liquid crystal cell element, and a passive liquidcrystal cell element.

As used herein the term “liquid crystal cell” refers to a structurecontaining a liquid crystal material that is capable of being ordered.Active liquid crystal cells are cells wherein the liquid crystalmaterial is capable of being switched between ordered and disorderedstates or between two ordered states by the application of an externalforce, such as electric or magnetic fields. Passive liquid crystal cellsare cells wherein the liquid crystal material maintains an orderedstate. One non-limiting example of an active liquid crystal cell elementor device is a liquid crystal display.

Examples of photochromic ophthalmic elements of the present inventioninclude, but are not limited to, corrective lenses, non-correctivelenses, contact lenses, intra-ocular lenses, magnifying lenses,protective lenses, and visors. Examples of display elements include, butare not limited to, screens, monitors, and security elements.

Further, the photochromic compounds according to various non-limitingembodiments of the present invention can have an average absorptionratio of at least 1.5 in an activated state as determined according toCELL METHOD. According to other non-limiting embodiments, thephotochromic compound can have an average absorption ratio ranging from4 to 20, 3 to 30, or 2.5 to 50 in an activated state as determinedaccording to CELL METHOD. According to still other non-limitingembodiments, the photochromic compounds can have an average absorptionratio ranging from 1.5 to 50 in an activated state as determinedaccording to CELL METHOD.

Reaction sequences for forming the photochromic compounds according tovarious non-limiting embodiments of the present invention having an Lgroup are disclosed in Reaction Sequences A through J, K, M, N, P, Q, Tin U.S. Pat. No. 7,342,112, which disclosure is incorporated herein byreference.

As discussed in the schemes outlined further below, compound 105represents one of the indenofused ring compounds described herein. Italso serves as the basis for preparing other indenofused ring compoundsdescribed herein. For example, it can be prepared as shown in Schemes 1,2, 3, 4 and 5. Once prepared, the hydroxy functionality of compound 106can be used for pyran formation and the halogen of 105 or one of itsprecursors 408 can be used for converting to Q′ as shown in Scheme 6.All structures from Scheme 6 are the indenofused ring compoundsdescribed herein.

Detailed chemical reactions that can be used for converting 106 to 604can be observed in Scheme 7, 8 and 9. Detailed chemical reactions forconverting the pyran dye 606 to 605 can be found in Scheme 10.

For all the indenofused ring compounds described in Schemes 1-5, X,which is a halogen group, was introduced into the structure beforeformation of the indenofused ring. The X group was then converted toanother member from which Q′ can be selected. Scheme 11 shows that X canalso be introduced into the indenofused ring compound after theformation of indenofused ring. Scheme 11 also shows that other membersfrom which Q′ can be selected, can be introduced into the structurewithout going through or requiring the presence of X.

In all schemes, X may be selected from halogen, e.g., F, Sr, Cl and I.Each t and i is an integer chosen from 0 to the total number ofavailable positions. From Scheme 1 to Scheme 6, R¹ for each occurrence,may be independently selected from hydrogen, halogen and optionallysubstituted chiral or achiral groups selected from alkyl,perfluoroalkyl, alkenyl, alkynyl, cycloalkyl, aryl, heteroaryl, alkoxy,perfluoroalkoxy, heteroalkyl, heterocycloalkyl, alkylthiol, arylthiol,amino aminocarbonyl, aryloxycarbonyl, alkyloxycarbonyl,aminocarbonyloxy, alkoxycarbonylamino, aryloxycarbonylamino,cycloalkoxycarbonylamino, heterocycloalkyloxycarbonylamino andheteroaryloxycarbonylamino. R² is selected from R¹.

Scheme 1 shows one way of preparing compound 105. R₃ and R₄ may beselected from optionally substituted chiral or achiral groups such asheteroalkyl, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl, and heterocycloalkyl.

The aryl ketone 101 can either be purchased or prepared byFriedel-Crafts methods or Grignard or Cuperate methods known in the art.For example, see the publication Friedel-Crafts and Related Reactions,George A. Olah, Interscience Publishers, 1964, Vol. 3, Chapter XXXI(Aromatic Ketone Synthesis); “Regioselective Friedel-Crafts Acylation of1,2,3,4-Tetrahydroquinoline and Related Nitrogen Heterocycles: Effect onNH Protective Groups and Ring Size” by Ishihara, Yugi et al, J. Chem.Soc., Perkin Trans. 1, pages 3401 to 3406, 1992; “Addition of GrignardReagents to Aryl Acid Chlorides: An efficient synthesis of aryl ketones”by Wang, Xiao-jun et al, Organic Letters, Vol. 7, No. 25, 5593-5595,2005, and references cited therein, which disclosures related to theaforementioned synthetic methods are incorporated herein by reference intheir entireties. A Stobbe reaction of aryl ketone 101 with dimethylsuccinate in the presence of potassium t-butoxide provides the condensedproduct of compound 102, which undergoes a ring closure reaction inacetic anhydride followed by methanolysis to form the product ofcompound 103.

Compound 103 can also be prepared from an ester-mediated nucleophilicaromatic substitution reaction starting from compound 106 by methodsknown to those skilled in the art, for example, as further described inSynthesis, January 1995, pages 41-43; The Journal of Chemistry SocietyPerkin Transaction 1, 1995, pages 235-241 and U.S. Pat. No. 7,557,208B2, which disclosures related to such synthetic methods are incorporatedherein by reference in their entireties.

Compound 103 can be further converted to the indeno-fused product ofcompound 105 with various substitutions on the bridge carbon via variousmultistep reactions that can be found in U.S. Pat. Nos. 5,645,767;5,869,658; 5,698,141; 5,723,072; 5,961,892; 6,113,814; 5,955,520;6,555,028; 6,296,785; 6,555,028; 6,683,709; 6,660,727; 6,736,998;7,008,568; 7,166,357; 7,262,295; 7,320,826 and 7,557,208, whichdisclosures related to the substituents on the bridge carbon areincorporated herein by reference in their entireties. Scheme 1illustrates that compound 103 reacts with Grignard reagent followed by aring closure reaction to provide compound 105.

Scheme 2 illustrates a second way of converting compound 103 to compound105. After hydrolysis of compound 103 followed by a ring closurereaction, compound 202 was obtained. The carbonyl of compound 202 canreact with a nucleophile, like a Grignard reagent, an Organo lithiumreagent, or a perfluoalkyl trimethylsilane to form compound 203. R³ maybe selected from optionally substituted chiral or achiral groups such asheteroalkyl, alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl,cycloalkyl and heterocycloalkyl. The hydroxyl group of compound 203 canbe converted into R⁴, which may be selected from halogen and optionallysubstituted chiral or achiral groups such as alkoxy, silanoxy,heteroaryloxy and aryloxy.

Scheme 3 illustrates a third way of converting compound 103 to compound105. Compound 202 from Scheme 2 can be reduced to 301 using aWolff-Kishner reduction or its modified version. Examples can be foundin “Practical procedures for the preparation ofN-tert-butyldimethylsilylhydrozones and their use in modifiedWolff-Kishner reductions and in the synthesis of vinyl halides andgem-dihalides” by Furrow, M. E., et al, J Am Chem Soc: 126(17): 5436-45,May 5, 2004, and references therein, which disclosures related to theWolff-Kishner reduction are incorporated herein by reference. Afterhydroxy protection, compound 302 has a very nucleophilic gem-carbon oncedeprotonated by base like LDA or methyl Grignard reagent. By thoseskilled in the art, the deprotonated compound 302 can be converted to R³and R⁴ substituted compound by reacting it with electrophiles such asalkyl halides, carbon dioxide, acid chlorides, nitriles andchloroformate derivatives. As a result, compound 105 can be preparedwith R³ and R⁴ selected from hydrogen, optionally substituted chiral orachiral groups selected from heteroalkyl, alkyl, cycloalkyl, carboxy,alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl, alkoxycarbonyl,aminocarbonyl, arylcarbonyl, aryloxycarbonyl, or R³ and R⁴ may be takentogether with any intervening atoms to form a group selected from oxo,optionally substituted cycloalkyl, and optionally substitutedheterocycloalkyl.

Schemes 4 and 5 summarize two novel methods of preparing compound 105,which are not believed to have been previously described.

Scheme 4 starts with aryl ketone 401. R₃ may be selected from hydrogen,optionally substituted chiral or achiral groups such as heteroalkyl,alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyland heterocycloalkyl.

After a Stobbe reaction with dimethyl succinate, compound 402 isconverted to an anhydride 403. This anhydride can be transformed into anindenone acid 404 with the use of aluminum chloride. A 1,4-additionreaction can be done with the use of nucleophiles like organometallicreagent, amine, alcohol and thiol. The reaction produces indano acid405. R₄ may be selected from hydrogen, optionally substituted chiral orachiral groups such as heteroalkyl, alkyl, alkenyl, alkynyl, aryl,heteroaryl, cycloalkyl, heterocycloalkyl, amino, alkoxy, and thiol.Compound 405 can be reacted with a Grignard reagent 406 to form compound407 after an acidic workup. Compound 407 undergoes a ring closurereaction in acetic anhydride followed by methanolysis to form product408, which can be either used directly in Scheme 6 or converted tocompound 105 by hydrolysis.

Scheme 5 starts with Stobbe product 102, which reacts with a Grignardreagent to provide compound 501. R₃ and R₄ may be selected fromoptionally substituted chiral or achiral groups such as heteroalkyl,alkyl, perfluoroalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyland heterocycloalkyl. After treating with bismuth triflate in tolueneand then acetic anhydride, two ring closure reactions occur in the samepot sequentially. The reaction results in compound 408, which can beconverted into compound 105.

Scheme 6 illustrates methods of converting compounds 105 (with —OH) or408 (with acetate) into other indenofused ring compounds. The hydroxygroup of 105 can be used in the chemistry for forming pyran dye 606, thehalogen of which can be converted to Q″′ as observed in Scheme 10.Halogen X of 105 can be converted to Q′ with the formation of compound604. Details are discussed in Schemes 7-9. Compound 604 can react with apropargyl alcohol to form pyran dye 605. The Q′ of 604 can also beconverted to a different Q′ represented by the lengthening group L. Whenthe Suzuki reaction is used, the Q″″ and A″ of the boronic acidderivative 601, together form a Q′ on 602. Methods for the synthesis ofthe boronic acid derivatives can be found from “Palladium(0)-CatalyzedCross-Coupling Reaction of Alkoxydiboron with Haloarenes: A DirectProcedure for Arylboronic Esters, J. Org. Chem. 60, page 7508-7519,1995” by Miyaura, Norio et als and references therein, which disclosuresrelated to such synthetic methods are incorporated herein by reference.As described herein, G may be —OH or —O-Alkyl; A″ may be selected fromaryl, alkenyl, alkynyl and heteroaryl; Q″″ may be selected from halogen,—OH, —N₃, —NR^(a)R^(a), —N(R^(a))C(O)Q″, —CN, —C(O)OR^(a), —C(O)R^(a),—C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a),—SR^(a), —OS(O₂)R^(b), C(O)NR^(a)R^(a) and a lengthening agent L. Thegroups Q″″ and A″ together form the Q′ group. B and B′ may be eachindependently selected from L, hydrogen, halogen, and optionallysubstituted chiral or achiral groups such as metallocenyl, alkyl orperfluoroalkyl, alkenyl, alkynyl, heteroalkyl, alkoxy, perfluoroalkoxy,aryl, heteroaryl, heterocycloalkyl, and cycloalkyl, or wherein B and B′are taken together with any intervening atoms to form a group such asoptionally substituted cycloalkyl and optionally substitutedheterocycloalkyl.

The group Q′ may be selected from halogen, —OH, —N₃, —NR^(a)R^(a),—N(R^(a))C(O)Q″, —CN, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a),—C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a), —SR^(a),—OS(O₂)R^(b), C(O)NR^(a)R^(a) and a lengthening agent L. The group Q′″may be selected from halogen, —OH, —N₃, —NR^(a)R^(a), —N(R^(a))C(O)Q″,—CN, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)),—OC(O)R^(a), —OC(O)OR^(a), —SR^(a), —OS(O₂)R^(b), and C(O)NR^(a)R^(a)

Schemes 7, 8 and 9 illustrate details of converting halogen to Q′. Thechemistries are done at hydroxy stage starting from compound 105, whichis shown as compound 701 representing a naphthol in Schemes 7 and 8. Theproduct of scheme 8, represented by compound 801 is used in Scheme 9 asthe starting material to form the compounds shown. Each of the hydroxyproducts of compounds 702, 706, 708, 709, 710, 802, 803, 807, 809, 810,811, 812, 901, 903, 904 and 906 can be converted to pyran photochromiccompounds using the propargyl alcohol chemistry shown in Scheme 6.

Scheme 10 shows the chemical reactions that can be done on thephotochromic dichroic dye. A″′ is a simplified representation of 606from Scheme 6. Scheme 10 demonstrates how to convert —X to -Q″′ groupssuch as cyano, aldehyde, carboxylic acid, and optionally substitutedchiral or achiral groups selected from imine, alkoxycarbonyl,aminocarbonyl and aryloxycarbonyl at the described position. Thecyanation and oxidation methods have been described in U.S. Patent Pub.No. 2009/0309076A1, wherein these cyanation and oxidation methods areincorporated herein by reference.

Schemes 1 to 5 have a halogen (X) incorporated into the startingmaterials and intermediates before formation of the indenofused ring.Also all non-halogen Q's in Schemes 6 to 10, are prepared eitherdirectly or indirectly through halogen intermediates. Scheme 11represents a method of incorporating X after formation of theindenofused ring structure. Scheme 11 also demonstrates the formation ofQ′ without going through starting materials or intermediates thatinclude halogen X.

Compound 1101 can be prepared using Scheme 5 as well as other schemes.Compared with the indenofused ring compounds described in the otherSchemes herein, Compound 1101 does not have a Q′ group attached thereto.The methoxy group in the structure is not limited to methoxy, and can bereplaced with other electron donating groups, such as other alkoxygroups, substituted amino groups and alkyl groups. When treated withN-Bromosuccinimide in DMF, the desired position is brominatedselectively to provide 1102. A Friedel-Crafts reaction can result in theformation or attachment of a Q′ group, such as acetyl, at the desiredposition, so as to provide 1103. Q′ can be converted to other Q′ groupsin either the pre-pyran stage or pyran stage as shown in Scheme 11. Forexample, a Baeyer-Villiger reaction can be used to convert the acetyl of1103 to the ester of 1104. The ester groups of 1104 can be subjected tohydrolysis resulting in formation of the hydroxy groups of 1105. Whenthe pyran ring of 1106 is formed, the hydroxyl at the Q′ position of1105 is not affected and is present in 1106. The same hydroxy isconverted to triflate by reaction with triflic anhydride in the presenceof a base, such as triethylamine. All compounds from 1103 to 1107 areprepared without going through one or more halogenated intermediates, incontrast to Schemes 1 to 10.

The present invention is more particularly described in the followingexamples, which are intended to be illustrative only, since numerousmodifications and variations therein will be apparent to those skilledin the art. Unless otherwise specified, all parts and all percentagesare by weight.

EXAMPLES

Part 1 describes the preparation of Examples 1-21 and 23-27corresponding to the naphthols and Examples 1A-5A, 9A, 10A, 13A-22A, 27Aand 28A corresponding to the indenonaphthopyran. Part 2 describes thetesting of the photochromic properties of the Examples 2A-5A, 10A, 13A,18A-22A, 27A and 28A.

In the examples below, the following abbreviations have the followingmeanings. If an abbreviation is not defined, it has its generallyaccepted meaning.

BI NAP=2,2′-bis(diphenylphosphino)-1,1′-binaphthyl

Bi(OTf)₃=bismuth triflate

CuI=copper iodide

DHP=3,4-dihydro-2H-pyran

DCC=dicyclohexylcarbodlimide

DCM=dichloromethane

DBSA=dodecylbenzenesulfonic acid

DIBAL=diisobutylaluminium hydride

DMAP=4-dimethylaminopyridine

DME=dimethyl ether

DMF=N,N-dimethylformamide

DMSO=dimethylsulfoxide

Dppf=1,1′-bis(diphenylphosphino)ferrocene

EtMgBr=ethyl magnesium bromide

Et₂O=diethylether

g=gram

h=hour

HPLC=high-performance liquid chromatography

(iPr)₂NH diisopropyl amine

HOAc=acetic acid

LDA=lithium diisopropylamide

KMnO₄=potassium permanganate

M=molar (molarity)

mCPBA=meta-Chloroperoxybenzoic acid

MeLi=methyl lithium

mg=milligram

min=minutes

mL=milliliter

mmol=millimoles

mM=millimolar

NatOBu=sodium tert-butoxide

N=normal (normality)

ng=nanogram

nm=nanometer

nM=nanomolar

NMP=N-methylpyrrolidone

NMR=nuclear magnetic resonance

Pd(OAc)₂=palladium acetate

Pd₂(dba)₃=tris(dibenzylideneacetone)dipalladium(0)

PPh₃=triphenyl phosphine

PPTS=pyridine p-toluenesulfonate

pTSA=p-toluenesulfonic acid

PdCl₂(PPh₃)₂=bis(triphenylphosphine)palladium(II) chloride

PBS=phosphate buffered saline

TBAF=Tetra-n-butylammonium fluoride

THF=tetrahyrdofuran

TLC=thin layer chromatography

t-BuOH=t-butanol

(Tf)₂O=trifluoromethanesulfonic acid anhydride

μL=microliter

μM=micromolar

Zn(OAc)₂=zinc acetate

Zn(CN)₂=Zinc cyanide

Part 1 Preparation of Examples Example 1

Step 1

A mixture of 4-bromoacetophenone (148 g), dimethyl succinic ester (130g) and toluene (2.5 L) was mechanically stirred in a suitable reactionflask. Potassium t-butoxide (100 g) was added in one portion and aprecipitate formed. After mixing one hour, water (1 L) was added. Therecovered aqueous layer was washed with toluene (200 ml) twice andacidified by 12 N HCl to pH of 2. The product was extracted with ethylacetate and then recrystallized from a mixture of ethyl ether/hexanes(1/1). White crystals (170 g) were obtained. NMR indicated that theproduct had a structure consistent with(E)-4-(4-bromophenyl)-3-(methoxycarbonyl)pent-3-enoic acid.

Step 2

The product from Step 1 (160 g) was mixed with 50 wt % sodium hydroxidewater solution (200 g) and water (4 liters) in a four liter beaker. Themixture was heated to boil and after one hour later the pH of thesolution was adjusted to about 2 using 12 N HCl. The resultingprecipitate was collected by filtration. Off-White crystals (152 grams)were obtained. NMR indicated that the product had a structure consistentwith (E)-2-(1-(4-bromophenyl)ethylidene)succinic acid.

Step 3

A mixture of the product from Step 2 (152 g), DBSA (5 g) and toluene (1L) was added to a reaction flask and heated up to reflux with waterremoval using a Dean-Stark trap, for two hours. The resulting mixturewas passed through a silica gel plug column and washed off the plugcolumn with 2/8 (v/v) ethyl aceate/hexanes, and concentrated. The typeof silica gel used in this and other examples was Grade 60, 230-400mesh. To the resulting oil, hexanes (1 L) was added. The productcrystallized and was collected by filtration and dried under vacuum.Off-white crystals (130 grams) were obtained. NMR indicated that theproduct had a structure consistent with(E)-3-(1-(4-bromophenyl)ethylidene)dihydrofuran-2,5-dione.

Step 4

To a stirred mixture of the aluminum chloride (130 g) and methylenechloride (1 L), the product from Step 3 (125 g) was added in threeportions over a 5 minute interval. After stirring at room temperaturefor 2 hours, HPLC showed that reaction was completed with the formationof two products. The reaction mixture was poured slowly into water (2L). Smoke generation was observed. A large amount of yellow solidformed. THF (1 L) was added to the mixture to dissolve the yellow solid.The water layer was saturated with solid NaCl and then removed by aseparatory funnel. The recovered organic layer was dried over magnesiumsulfate and concentrated. Ethyl acetate (200 mL) was added and theyellow crystals that formed were collected and dried (50 grams). NMRindicated that the product had a structure consistent with2-(6-bromo-3-methyl-1-oxo-1H-inden-2-yl)acetic acid.

Step 5

A reaction flask containing a mixture of manganese chloride (7.46 g) andlithium chloride (5 g) was dried at 200° C. in a vacuum oven for anhour. Under the protection of nitrogen, THF was added (200 mL). After 30minutes, copper (I) chloride (0.59 g) and the product from Step 4 (19.4g) were added. The mixture was stirred until clear and cooled to 0° C.To the resulting mixture, a 2M THF solution of butyl magnesium bromide(99 mL) was added dropwise over 2 hours. After the addition, the mixturewas stirred at 0° C. for 2 hours and water (200 mL) was added. The pH ofthe mixture was adjusted to ˜2 using 12 N HCl. Ethyl acetate (200 mL)was added. The recovered organic portion was dried, and concentrated.The product was purified by CombiFlash® Rf from Teledyne ISCO. Oil (4 g)was obtained as the product. NMR indicated that the product had astructure consistent with2-(5-bromo-1-butyl-1-methyl-3-oxo-2,3-dihydro-1H-inden-2-yl)acetic acid.

Step 6

Solid magnesium (1.5 g) was placed in a reaction flask equipped with adropping funnel and dried in an oven. THF (60 mL) and1-bromo-4-trifluoromethylbenzene (15.3 g) were added. With theinitiation of one drop of 1,2-dibromoethane, Grignard reagent started toform. An ice bath was used to control the temperature around roomtemperature. After two hours a solution of the product from Step 5 (4.2g) in anhydrous THF (20 mL) was put into the dropping funnel and addedto the reaction mixture over a 10 minute interval. After the addition,the mixture was stirred at room temperature for 2 hours and water (100mL) was added. The pH was adjusted to about 2 using 12 N HCl. Ethylacetate (100 mL) was added and the resulting organic phase was collectedby a separatory funnel, washed with NaCl/water, dried over magnesiumsulfate and concentrated. The obtained oil was re-dissolved in toluene(100 mL) in a reaction flask. Acetic anhydride (10 grams) and bismuthtriflate (0.5 g) was added. The mixture was refluxed for 1 hour andcooled to room temperature. Methanol (100 mL) and 12 N HCl (1 mL) wasadded. The mixture was refluxed for 12 hours. All the solvent wasremoved. A silica gel plug column separation was applied to the crudeproduct. Oil (3 g) was obtained as the product. NMR indicated that theproduct had a structure consistent with10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.

Example 1A

The product from Step 6 (3 g) of Example 1 was placed in a reactionflask. To the flask,1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol (2.1 g),1,2-dichloroethane (30 mL) and p-toluenesulfonic acid (70 mg) wereadded. The mixture was refluxed for 4 hours. All solvent was removed. Asilica gel plug column was used to purify the product. A brownish oil (2grams) was obtained as the product. NMR indicated that the product had astructure consistent with3-(4-fluorophenyl)-3-(4-(N-morpholino)phenyl)-10-bromo-6-trifluoromethyl-13-methyl-13-butyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 2

The procedures from Example 1 were followed except that: in Step 5, 1.4M THF solution of methyl magnesium bromide was used in place of butylmagnesium bromide; and in Step 6,1-bromo-4-trifluoromethoxybenzene wasused in place of 1-bromo-4-trifluoromethylbenzene. NMR indicated thatthe product had a structure consistent with10-bromo-7,7-dimethyl-3-(trifluoromethoxy)-7H-benzo[c]fluoren-5-ol.

Example 2A

The procedures from Example 1A were followed except that:10-bromo-7,7-dimethyl-3-(trifluoromethoxy)-7H-benzo[c]fluoren-5-ol fromExample 2 was used in place of10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol;1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMRindicated that the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10-bromo-6-trifluoromethoxy-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 3

The procedures from Example 1 were followed except that in Step6,1-bromo-4-fluorobenzene was used in place of1-bromo-4-trifluoromethylbenzene. NMR indicated that the product had astructure consistent with10-bromo-7-butyl-3-fluoro-7-methyl-7H-benzo[c]fluoren-5-ol.

Example 3A

The procedures from Example 1A were followed except that:10-bromo-7-butyl-3-fluoro-7-methyl-7H-benzo[c]fluoren-5-ol from Example3 was used in place of10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol;1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMRindicated that the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10-bromo-6-fluoro-13-methyl-13-butyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 4

The procedures from Example 1 were followed except that in Step6,1-bromo-3,5-difluorobenzene was used in place of1-bromo-4-trifluoromethylbenzene. NMR indicated that the product had astructure consistent with10-bromo-7-butyl-2,4-difluoro-7-methyl-7H-benzo[c]fluoren-5-ol.

Example 4A

The procedures from Example 1A were followed except that:10-bromo-7-butyl-2,4-difluoro-7-methyl-7H-benzo[c]fluoren-5-ol fromExample 4 was used in place of10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol;1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMRindicated that the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10-bromo-5,7-difluoro-13-methyl-13-butyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 5

Step 1

A 2 L flask with tribromobenzene (100 g) and a magnetic stir bar wasdried in a vacuum oven at 80° C. for 4 hours, Dry THF (500 ml) wasadded. The resulting mixture was placed in an NaCl saturated ice bath.3M Isopropyl magnesium chloride (160 ml) was added drop wise to thesolution at a rate so that the inside temperature was controlled to −20to 0° C. The addition was finished in about 30 minutes to 1 hour. Themixture was stirred for half an hour at the same temperature andbis[2-(N,N-dimethylamino)ethyl]ether (61 g) was added slowly over a 5minutes interval and a large amount of precipitate formed. The resultingmixture was stirred for 20 more minutes and a mixture of4-trifluoromethylbenzoyl chloride (73 g) and THF (100 ml) was added overa 5 minute interval. The resulting mixture was stirred overnight. Water(100 ml) was added slowly and the pH was adjusted to 2 with 3N HCl. Theorganic layer was collected by a separatory funnel, washed with 5%NaOH/water and NaCl/water, dried and concentrated. To the recovered oil,methanol (300 ml) was added and the product crystallized. The productwas collected by filtration. NMR showed that the obtained white crystals(87 g) have a structure consistent with3,5-dibromo-4′-trifluoromethylbenzophenone.

Step 2

A mixture of 3,5-dibromo-4′-trifluoromethylbenzophenone (75 g) from Step1, dimethyl succinic ester (32.2 g) and toluene (800 ml) were placed ina three neck 5 L flask equipped with a mechanical stir. Solid ofpotassium t-butoxide (22.6 g) was added batchwise over a 30 minuteinterval. An exothermic reaction along with the formation of a largeamount of precipitate was observed. After two hours, water (500 ml) wasadded and a milky mixture was obtained. The pH of the mixture wasadjusted to ˜2 using 3 N HCl. After stirring at room temperature for 10minutes, the organic layer was collected, washed with NaCl/HCl, driedover MgSO4. After concentration, hexanes were added and white crystalsformed. The crystals were collected by filtration. NMR showed that theobtained product (62 grams) had a structure consistent with(E)-4-(3,5-dibromophenyl)-3-(nnethoxycarbonyl)-4-(4-(trifluoromethyl)phenyl)but-3-enoicacid.

Step 3

Solid anhydrous lanthanum (III) chloride (100 g) was ground to a veryfine powder and then mixed with lithium chloride (52 g) and dry THF (1liter) in a 5 liter three-neck flask equipped with a mechanical stir anda dropping funnel. The mixture was refluxed for few hours until itdissolved. Solid(E)-4-(3,5-dibromophenyl)-3-(methoxycarbonyl)-4-(4-(trifluoromethyl)phenyl)but-3-enoicacid (106 g) from Step 2 was dissolved in the mixture. The mixture wasthen cooled to −15° C. A solution of 3M methyl magnesium chloride (238ml) was placed in the dropping funnel. The first 30% of the Grignard wasadded slowly to the mixture. Generation of gas bubbles was observed.After the temperature returned to −15° C., the remainder of the Grignardwas added to the mixture in 2 minutes. After 30 minutes, water (1 L) wasadded slowly to the mixture and the pH was adjusted to acidic usingacetic acid. The mixture turned clear with formation of two layers.Water layer was drained off. Organic layer was washed with NaCl/waterfour times and then concentrated to dry. A light yellowish solid wasrecovered and dissolved in toluene. The solution was filtered using asilica gel plug column and the recovered clear solution was concentratedto dryness. White solid product was obtained and used in the next Stepwithout further purification. A portion of the product wasrecrystallized from methanol and NMR analysis showed that the purifiedcrystals had a structure consistent with(E)-4-((3,5-dibromophenyl)(4-(trifluoromethyl)phenyl)methylene)-5,5-dimethyldihydrofuran-2(3H)-one.

Step 4

Into a reaction flask was added the product from Step 3, toluene (500ml), bismuth triflate (20 g) and acetic acid (0.24 g). The resultingmixture was stirred at reflux for 1 hour. After it cooled to roomtemperature, acetic anhydride (100 ml) was added. The mixture was heatedto reflux again and after one hour, the mixture was cooled to roomtemperature and filtered through a silica gel plug column. The recoveredclear solution was concentrated to dryness. Acetone (50 ml) was added tothe obtained solid to form a slurry and methanol (250 ml) wassubsequently added. The resulting mixture was cooled to form crystals.The recovered white crystals (58 g) were analyzed by NMR which showedthat the product had a structure consistent with8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate.

Step 5

To a flask containing8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate (2.42 g) from Step 4 was added methanol (20 mL) andtetrahydrofuran (10 mL). Concentrated hydrochloric acid (1 mL) was addedand the solution was heated to reflux for 4 h. The solvent was removedunder vacuum and the residue was purified by filtration through a plugof silica gel, using 4:1 hexane/ethyl acetate mixture as the eluent.Fractions containing the desired material were grouped and concentratedto provide a cream colored solid (1.63 g). NMR analysis of the creamcolored solid indicated a structure that was consistent with8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.

Example 5A

To a chloroform solution (100 mL) of the product from Step 5 of Example5, (36.24 g) was added1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol (28.00 g) and4-dodecylbenzenesulfonic acid (2.40 g). The solution was heated toreflux for 8 h. The reaction mixture was concentrated under reducedpressure to provide an oily residue. The residue was purified by columnchromatography using 9:1 hexane ethyl acetate mixtures as the eluant.Fractions containing the desired material were grouped and concentratedto an oily residue. The residue was re-crystallized from dichloromethaneand methanol. The crystals were collected by vacuum filtration and driedto provide a grey solid (20.00 g). NMR analysis of the grey solidindicated a structure that was consistent with3-(4-butoxyphenyl)-3-(4-methoxyphenyl)-10,12-dibromo-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 6

8,10-Dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate (53.88 g) from Step 4 of Example 5 and4′-(4-trans-pentylcyclohexyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1′-biphenyl]-4-carboxamide(56.27 g) were dissolved in a reaction flask containing a 1:1 mixture oftoluene (1000 mL) and ethanol (1000 mL). Potassium carbonate (42.26 g)and triphenylphosphine (8.02 g) were added and the solution was degassedby bubbling nitrogen for 20 min. Palladium acetate (2.29 g) was addedand the mixture was heated to reflux for 3 h. The reaction mixture wascooled to room temperature and a degassed suspension ofbis(triphenylphosphine)palladium(II) chloride (7.15 g) in toluene (100mL) and ethanol (100 mL) was added. The reaction mixture was heated toreflux for 16 h. The reaction mixture was cooled to room temperature anddiluted with ethyl acetate (500 mL). The mixture was filtered through abed of CELITE® filter aid and the filtrate was collected andconcentrated in vacuo to provide a residue. The residue was purified bycolumn chromatography using 19:1 toluene and ethyl acetate mixture asthe eluant. Fractions that contained the desired product were groupedand concentrated in vacuo to provide a cream colored residue. Toluenewas added to the residue to precipitate the product. The resultingprecipitate was collected by vacuum filtration and dried to provide acream colored solid (32 g). NMR analysis of the cream colored solidindicated a structure that was consistent7,7-dimethyl-3-trifluoromethyl-10-[4-(4-(4-(4-trans-pentylcyclohexyl)phenyl)benzamido)phenyl]-7H-benzo[c]fluoren-5-ol.

Example 7

Step 1 to Step 4

Procedures from Steps 1 to 4 of Example 5 were followed except that inStep 1,3,5-dichlorobromobenznene and 4-methoxybenzoyl chloride was usedin place of tribromobenzene and 4-trifluoromethylbenzoyl chloride. Anoff-white solid was obtained as the product. NMR indicated that theproduct had a structure consistent with2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-yl acetate.

Step 5

A mixture of the product from Step 4 (5 g), NBS (2.7 g) and DMF (100 mL)was stirred in a reaction flask and heated to 90° C. Two hours later,the reaction mixture was poured into water (400 mL) and extracted with1/1 ethyl acetate/THF (200 mL). The organic layer was collected, washedwith sodium bisulfite water solution three times, dried andconcentrated. To the recovered product, methanol (100 mL) was added.After filtration, an off white solid (4.4 g) was obtained as theproduct. NMR indicated that the product had a structure consistent with10-bromo-2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ylacetate.

Example 8

A mixture of the product of Example 7,10-bromo-2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ylacetate (4.3 g),4′-(4-trans-pentylcyclohexyl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)-[1,1′-biphenyl]-4-carboxamide(4.94 g), sodium carbonate (4 g), THF (200 mL), water (20 mL) andTetrakis(triphenylphosphine)palladium(0) (1 g) was placed in a reactionflask and degassed by bubbling nitrogen through the mixture for 10minutes. The mixture was heated to reflux for 17 hours. Potassiumcarbonate (5 g) and ethanol (50 mL) was added and the resulting mixturewas refluxed for 8 hours, extracted using THF and sodium chloridesaturated water. The resulting organic layer was collected, washed with100 mL 1 N HCl three times, washed with 100 mL 1 N sodium sulfite watersolution once, washed with sodium chloride saturated water once, driedover magnesium sulfate and concentrated. The recovered residue wasdissolved in 10/1 (v/v) toluene/THF (200 mL) and passed through a silicagel plug column which was washed using 10/1 toluene/INF to recover theproduct. The resulting clear solution was concentrated and added tomethanol and stirred for half an hour. The resulting solid was collectedand dried to provide an off-white solid (7.5 g) as the product. NMRindicated that the product had a structure consistent with2,4-dichloro-7,7-dimethyl-9-methox-10-[4-(4-(4-(4-trans-pentylcyclohexyl)phenyl)benzamido)phenyl]-7H-benzo[c]fluoren-5-ol.

Example 9

The procedures from Example 5 were followed except that in Step1,3,5-difluorobenzoyl chloride was used in place of4-trifluoromethylbenzoyl chloride to produce in Step 5, the desiredproduct which was recrystallized using ethyl acetate as the solvent. NMRindicated that the product had a structure consistent with8,10-dibromo-2,4-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-ol.

Example 9A

The procedures from Example 1A were followed except that:8,10-dibromo-2,4-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-ol fromExample 9 was used in place of10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-oland 1-(4-fluorophenyl)-1-(4-(N-piperidinyl)phenyl)prop-2-yn-1-ol wasused in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMR showedthat the product had a structure consistent with3-(4-fluorophenyl)-3-(4-(N-piperidinyl)phenyl)-10,12-dibromo-5,7-difluoro-13,13-dimethyl-butyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 10

The procedures from Example 5 were followed except that in Step1,2,4-difluorobenzoyl chloride was used in place of4-trifluoromethylbenzoyl chloride. NMR analysis indicated that theproduct had a structure consistent with8,10-dibromo-1,3-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-ol.

Example 10A

The procedures from Example 1A were followed except that8,10-dibromo-1,3-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-ol was usedin place of10-bromo-7-butyl-7-methyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-oland 1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-fluorophenyl)-1-(4-(N-morpholino)phenyl)prop-2-yn-1-ol. NMR showedthat the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10,12-dibromo-6,8-difluoro-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 11

The procedures from Step 1 to Step 4 of Example 5 were followed exceptthat in Step 1, 2,5-difluorobenzoyl chloride was used in place of4-trifluoromethylbenzoyl chloride. NMR analysis indicated that theproduct had a structure consistent with8,10-dibromo-1,4-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-yl acetate.

Example 12

Procedures Example 6 were followed except that8,10-dibromo-1,4-difluoro-7,7-dimethyl-7H-benzo[c]fluoren-5-yl acetatewas used in place of8,10-Dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate. NMR analysis of the solid indicated a structure consistent with7,7-dimethyl-1,4-difluoro-10-[4-(4-(4-(4-trans-pentylcyclohexyl)phenyl)benzamido)phenyl]-7H-benzo[c]fluoren-5-ol.

Example 13

Step 1

Magnesium (3.9 g) and THF (50 mL) was placed in a dry flask equippedwith a dropping funnel, which contained a THF (800 mL) solution of2,4,6-tribromotoluene (53 g). One tenth of the THF solution in thedropping funnel was added to the flask and the reaction flask started toboil. The reaction flask was placed in an ice bath was applied and thereaction mixture was maintained at 0° C. and the remainder of thesolution in the dropping funnel was added drop wise over a half an hour.After stirring 1.5 h, bis[2-(N,N-dimethylamino)ethyl]ether (28.4 g) wasadded. After stirring for one hour, 3,4-dimethoxybenzoyl chloride (35.5g) was added in one portion. The resulting mixture was stirredovernight, water (500 mL) was added to the mixture and 12N HCl was usedto adjust pH to ˜2. DCM was added to the mixture (500 mL) and theresulting organic layer was collected, washed with water once, washedwith sodium bicarbonate once, dried over magnesium sulfate andconcentrated. A yellow oil (65 g) was obtained. The oil was useddirectly in the next step.

Step 2

The product from Step 1 (65 g), dimethyl succinate (30 g) and toluene(500 mL) were added to a reaction flask equipped with a mechanicalstirrer, a dropping funnel and a nitrogen blanket. The mixture wasstirred at room temperature until the solids were dissolved. A toluenesolution of potassium t-pentoxide (25 wt %, 87.4 g) was added through adropping funnel and the mixture was stirred at room temperature for 2hours. The resulting reaction mixture was poured into 1 L of water andthe aqueous layer, which contained the product, was collected. Thetoluene layer was extracted with 200 mL water. The combined waterextracts was washed with toluene. HCl (12 N) was added to the waterextracts until pH was adjusted to 5. A yellow oil precipitated. Theresulting mixture was extracted with ethyl acetate, dried over magnesiumsulfate, concentrated and dried in vacuum. A yellow glassy oil (35 g)was obtained as product. It was used directly in the next step.

Step 3

A mixture of the Stobbe acid products from Step 2 (35 g), bismuthtriflate (2.1 g), dichloromethane (200 mL) and acetic anhydride (27 g)was mixed and stirred at room temperature in a reaction flask for onehour. The resulting mixture was concentrated by vacuum evaporation andmethanol (500 mL) and HCl (12 N, 2 mL) were added. The resulting mixturewas refluxed for 4 hours and concentrated to provide an oil. The oil waspassed through a silica gel plug column separation followed byrecrystallization from 2/8 (v/v) ethyl acetate/hexane. White crystals (5g) were obtained as the product. NMR indicated that the product had astructure consistent with methyl1-(3,5-dibromo-4-methylphenyl)-4-hydroxy-6,7-dimethoxy-2-naphthoate.

Step 4

The product from Step 3 (1.5 g) was dissolved in 30 mL of anhydrous THFin an oven dried flask equipped with a dropping funnel and a magneticstir bar. The mixture was stirred at room temperature, and 7 mL 3 M THFsolution of methyl magnesium bromide was added dropwise. After theaddition, the mixture was stirred at room temperature for overnight. Thereaction mixture was then poured into 100 mL water. The pH value of themixture was adjusted to ˜5 using HCl (12 N). Ethyl acetate (100 mL) wasadded. The resulting organic layer was separated, dried over magnesiumsulfate, concentrated and dried in vacuum. The recovered white solid(1.5 g) was used directly in the next step.

Step 5

The product from Step 4 (1.5 g), toluene (100 mL) and bismuth triflate(0.04 g) were added to a reaction flask equipped with a magnetic stirbar. The resulting mixture was refluxed for 4 hours. The reactionmixture was passed through a silica gel plug column. Afterconcentration, white solid (0.8 g) was obtained. NMR indicated that thewhite solid had a structure consistent with8,10-dibromo-2,3-dimethoxy-7,7,9-trimethyl-7H-benzo[c]fluoren-5-ol.

Example 13A

To a reaction flask containing a toluene solution (20 ml) of the productfrom Example 13 (0.8 g) 1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (0.8 g)and a few crystals of p-toluene sulfonic acid were added. After stirringfor one hour at room temperature, all solvent was evaporated. Therecovered product was purified by CombiFlash®Rf followed byrecrystallization from ether ether. White crystals (0.95 g) wereobtained as the product. NMR indicated that the product had a structureconsistent with3,3-bis(4-methoxyphenyl)-10,12-dibromo-6,7-dimethoxy-11,13,13-trimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 14A

Step 1

To a mixture of degassed dioxane (100 mL) and toluene (100 mL) in areaction flask was added 2,2′-bis(diphenylphosphino)-1,1′-binaphthyl(1.20 g) and palladium (II) acetate (0.30 g). The product from Step 4 ofExample 5,8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate (5.10 g) was added followed by 1-formylpiperazine (2.80 g) undera stream of nitrogen. Sodium Pert-butoxide (2.80 g) was added and thesolution was heated to reflux for 22 h. The reaction mixture was cooledto room temperature and diluted with tetrahydrofuran. The solution wasfiltered through a bed of CELITE® filter aid and the filtrate wasconcentrated under vacuum. The residue was purified by columnchromatography using 1:4 (v:v) methylene chloride and ethyl acetatemixtures as the eluant. Fractions containing the desired material weregrouped and concentrated. The residue (1.25 g) was used directly for thenext step. NMR analysis of the residue indicated a structure that wasconsistent with4-(8-bromo-5-hydroxy-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-10-yl)piperazine-1-carbaldehyde.

Step 2

The product of Step 1, (0.69 g) and1-(4-butoxyphenyl)-1-(4-fluorophenyl)prop-2-yn-1-ol (0.60 g) weredissolved in 1,2-dichloroethane (20 mL) in a reaction flask.p-Toluenesulfonic acid (0.1 g) was added and the solution was heated toreflux for 18 h. The reaction mixture was cooled to room temperature andthe solvent was removed in vacuo. The residue was purified by columnchromatography using 1:1 hexanes and dichloromethane mixtures as theeluant. Fractions containing the desired material were grouped andconcentrated. The residue (0.75 g) was used directly in the next step.

Step 3

The product of Step 2 (2.00 g) was dissolved in dioxane (30 mL) in areaction flask. 10% HCl aq (5 mL) was added and the solution was heatedto reflux for 2 h. The reaction mixture was cooled to room temperatureand poured into a saturated aqueous sodium bicarbonate solution (300mL). The recovered aqueous layer was extracted with ethyl acetate (300mL). The ethyl acetate solution was dried with anhydrous sodium sulfate,filtered and concentrated to provide a residue. The residue was purifiedby column chromatography using 1:1 (v:v) ethyl acetate and methanolmixture as the eluant. Fractions containing the desired material weregrouped and concentrated. The residue was collected as the product. NMRindicated that the structure was consistent with3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(piperazin-1-yl)-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 15A

Step 1

The procedure from Example 5A was followed except that1-(4-fluorophenyl)-1-(4-butoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol. NMR analysis ofthe purple colored product indicated a structure that was consistentwith3-(4-butoxyphenyl)-3-(4-fluorophenyl)-10,12-dibromo-6-trifluoromethyl-13,13-dimethyl-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Step 2

To a mixture of the product of Step 1 (2.00 g) and4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (0.57 g) in 1:1mixture of THF (25 mL) and water (25 mL) in a reaction flask was addedpotassium fluoride (1.5 g). The solution was degassed by bubblingnitrogen for 10 min. To the degassed solution, bis(triphenylphosphine)palladium(II) chloride (0.25 g) was added. The solution was heated toreflux for 8 h. The reaction mixture was cooled to room temperature anddiluted with ethyl acetate. The mixture was then filtered through a bedof CELITE® filter aid and the filtrate was partitioned with ethylacetate and water. The ethyl acetate extract was collected, dried withanhydrous sodium sulfate and concentrated to provide an oily residue.The residue was purified by column chromatography using 9:1 (v:v) hexaneand ethyl acetate mixture as the eluant. Fractions that contained thedesired product were grouped and concentrated in vacuo to provide anoily residue. The oil was dissolved in a minimum amount ofdichloromethane and added drop-wise to a vigorously stirred solution ofmethanol. The resulting precipitate was collected by vacuum filtrationand dried to provide a solid (1.00 g). NMR analysis of the solidindicated a structure that was consistent with3-(fluorophenyl)-3-(4-butoxyphenyl)-10-(4-hydroxyphenyl)-6-trifluoromethyl-12-bromo-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 16

To a three neck round bottom flask (100 mL) were addedbis(dibenzylideneacetone)plalladium(0) (0.55 g),2-di-tert-butylphosphino-3,4,5,6-tetramethyl-2′,4′,6′-triisopropyl-1,1′-biphenyl(1.14 g), crushed potassium phoshate (8.72 g),8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate from Step 4 of Example 5 (5.00 g) and 4-hydroxybenzamide (2.15g). The flask was evacuated and filled with nitrogen. Degassedtert-butanol (30 mL) was added and the mixture was heated to reflux for6 h. The reaction mixture was cooled to room temperature and dilutedwith EtOAc. The solution was filtered through a bed of CELITE® filteraid and the filtrate was collected. The filtrate was concentrated andthe residue was purified by column chromatography using 4:1 (v:v) ethylacetate and hexanes mixture as the eluant. Fractions containing thedesired material were grouped and concentrated to provide an oil. Theoil was added to a minimum amount of ethyl acetate and hexanes wasadded, and the flask was scratched to provide crystals. The crystalswere collected by vacuum filtration and dried to provide a white coloredsolid (4.27 g). NMR analysis of the white colored solid indicated astructure that was consistent with8-bromo-7,7-dimethyl-3-trifluoromethyl-10-(4-hydroxybenzamido)-7H-benzo[c]fluoren-5-ol.

Example 16A

The procedure from Example 5A was followed except that1-(4-fluorophenyl)-1-(4-butoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol and the productfrom Example 16 was used in place of8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.NMR analysis of the cream colored solid indicated a structure that wasconsistent with3-(fluorophenyl)-3-(4-butoxyphenyl)-10-(4-hydroxybenzamido)-6-trifluoromethyl-12-bromo-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 17

8-Bromo-7,7-dimethyl-3-trifluoromethyl-10-(4-hydroxybenzamido)-7H-benzo[c]fluoren-5-ol(5.00 g) from Example 16, potassium carbonate (5.10 g), 2-butanol (50mL) and methanol (50 mL) were added to a round bottom flask and degassedfor 10 min. Tetrakistriphenylphosphine palladium (0) (0.55 g) was addedand heated to reflux under nitrogen for 2 h. The reaction mixture wascooled to room temperature and filtered through a bed of CELITE® filteraid. The filtrate was concentrated and the residue was purified bycolumn chromatography using 4:1 (v:v) ethyl acetate and hexanes mixtureas the eluant. Fractions containing the desired material were groupedand concentrated to provide a foam (4.00 g). NMR analysis of the foamindicated a structure that was consistent with4-hydroxy-N-(5-hydroxy-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-10-yl)benzamide.

Example 17A

The procedure from Example 5A was followed except that1-(4-fluorophenyl)-1-(4-butoxyphenyl)prop-2-yn-1-ol was used instead of1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol and the productfrom Example 17 was used in place of8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.NMR analysis of the cream colored solid indicated a structure that wasconsistent with3-(fluorophenyl)-3-(4-butoxyphenyl)-10-(4-hydroxybenzamido)-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 18

Step 1

Magnesium (5.38 g) and THF (50 mL) was placed in a dry flask equippedwith a dropping funnel which contained a mixture of1-bromo-3,5-dichlorobenzene (50 g) and THF (300 mL). 30 mL of thesolution in the dropping funnel was added to the flask. A few drops ofdibromoethane were also added to the flask and a few minutes later,solvent in the reaction flask started to boil. The remainder of thesolution in the dropping funnel was added drop wise. Ice water was usedoccasionally to help the reaction mixture to stay at around roomtemperature. After the addition, the mixture was stirred at roomtemperature for two hours. Benzonitrile (22.82 g) was added to thereaction mixture and the mixture was refluxed for 2 days. 3 N HCl (300mL) was added and the mixture was stirred for 4 hours and then extractedusing ethyl acetate. The organic layer was collected and thenconcentrated. The recovered oil (49 g) was used in the next step withoutfurther purification.

Step 2

The product from Step 1 (47 g), dimethyl succinate (36 g) and toluene(500 mL) were added to a reaction flask equipped with a mechanicalstirrer, a solid addition funnel and a nitrogen blanket. The mixture wasstirred at room temperature until the solids were dissolved. Solidpotassium t-butoxide (23.1 g) was added through the solid additionfunnel and the mixture was stirred at room temperature for 4 hours. Theresulting reaction mixture was poured into 1 L of water and the aqueouslayer, which contained the product, was collected. The toluene layer wasextracted with 200 mL water. The combined water solution was washed withtoluene. HCl (3 N) was added to the water solution to adjust the pH to5. The resulting mixture was extracted with ethyl acetate, dried overmagnesium sulfate, concentrated and dried in vacuum. Oil was obtained asproduct (65 g). It was used directly in the next step.

Step 3

A mixture of the product (65 g) from Step 2 and acetic anhydride (200mL) was mixed and refluxed in a reaction flask equipped with acondenser. After one hour, the acetic anhydride was removed by vacuumevaporation and the obtained oil (67 g) was used directly in the nextstep.

Step 4

To a reaction flask containing the product of Step 3 (67 g) was addedmethanol (500 mL) of and HCl (12 N, 1 mL). The mixture was refluxed fortwo hours. Methanol was removed by vacuum evaporation. The recovered oilwas dissolved in methylene chloride, washed with sodium bicarbonatesaturated water, dried over magnesium sulfated, concentrated and driedin vacuum. Clear oil (48 g) was obtained. Ethyl acetate/hexane (1/9)((v/v) was used to crystallize the product. White crystals (12 g) wereobtained as the undesired regio-isomer. The mother liquor wasconcentrated. Oil (31 g) was obtained. NMR indicated that majority ofthe product in the oil (80%) had a structure consistent with methyl1-(3,5-dichlorophenyl)-4-hydroxy-2-naphthoate.

Step 5

The product (31 g) from Step 4 was dissolved in anhydrous THF (500 ml)in an oven dried flask equipped with a dropping funnel and a magneticstir bar. The mixture was stirred mixture at room temperature, and 1.6 Mtoluene/THF (1:1) solution of methyl magnesium bromide (160 ml) wasadded dropwise. After the addition, the mixture was stirred at roomtemperature for about 16 hours. The reaction mixture was then pouredinto 2 L of ice water. The pH value of the mixture was adjusted to ˜2using HCl (12 N). Ethyl acetate (500 mL) was added. The resultingorganic layer was separated, dried over magnesium sulfate, concentratedand dried in vacuum. The recovered product (30 g of oil) was useddirectly in the next step.

Step 6

The product from Step 5 (30 g) and xylene (300 were added to a reactionflask equipped with a magnetic stir bar. p-Toluenesulfonic acid (1 g)was added and the resulting mixture was refluxed for eight hours. Xylenewas removed by vacuum evaporation and the resulting oily product wasdissolved in ethyl acetate, washed with water, dried over magnesiumsulfate and concentrated. The crude product was obtained as oil (20 g).A small portion of the product (1.8 g) was purified using a CombiFlashRf from Teledyne ISCO. After separation, two components were obtained.NMR analysis showed the major component had a structure consistent with:8,10-dichloro-7,7-dimethyl-7H-benzo[c]fluoren-5-ol.

Example 18A

The crude product from Step 6 of Example 18 (18 g) was placed in areaction flask. To the flask was added of1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (20 g), a few crystals ofp-toluenesulfonic acid and methylene chloride (300 ml). The mixture wasstirred at room temperature for one hour. The product was purified usinga CombiFlash® Rf from Teledyne ISCO followed by a recrystallization fromethyl ether. A grey solid (10 g) was obtained as the product. NMRanalysis indicated that the product had a structure consistent with3,3-bis(4-methoxyphenyl)-10,12-dichloro-13,13-trimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 19

Triphenylphosphine (2.23 g) and palladium acetate (0.64 g) were added toa degassed mixture of toluene (30 mL) and ethanol (30 mL).8,10-Dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ylacetate (15.00 g) from Step 4 of Example 5 and vinylboronic pinacolester (8.75 g) were added and the solution was degassed by bubblingnitrogen for 10 min. Potassium carbonate (11.75 g) was added and themixture was heated to reflux for 18 h. The reaction mixture was cooledto room temperature and carefully poured into 10% aqueous HCl. Themixture was stirred for 10 min and the aqueous was partitioned withEtOAc. The EtOAc extract was washed with saturated sodium bisulfite. TheEtOAc extract was then filtered through Celite. The filtrate wasconcentrated under vacuum to provide a residue. The residue was purifiedby a plug of silica and eluting with 9:1 hexane:EtOAc. Fractionscontaining the desired material were grouped and concentrated to providea white solid (8 g). NMR analysis of the white solid indicated astructure that was consistent with8-bromo-7,7-dimethyl-3-trifluoromethyl-10-vinyl-7H-benzo[c]fluoren-5-ol.

Example 19A

The procedure from Example 5A was followed except that1-(4-fluorophenyl)-1-(4-butoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol and the productfrom Example 19 was used in place of8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.NMR analysis of the cream colored solid indicated a structure that wasconsistent with3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-vinyl-6-trifluoromethyl-12-bromo-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 20

The product from Step 1 of Example 19,8-bromo-7,7-dimethyl-3-(trifluoromethyl)-10-vinyl-7H-benzo[c]fluorenol(8.44 g), potassium carbonate (10.75 g), 2-butanol (20 mL) and methanol(20 mL) were added to a round bottom flask (100 mL) and degassed for 10min. Bis(triphenylphosphine)palladium(II)chloride (0.7 g) was added andheated to reflux for 18 h. The reaction mixture was cooled to roomtemperature and carefully poured into 10% HCl. The mixture was dilutedwith ethyl acetate and partitioned. The ethyl acetate extract was washedwith sodium bisulfite and dried with sodium sulfate. The ethyl acetatesolution was then filtered through a bed of Celite and the filtrate wasconcentrated. The residue was purified by column chromatography using9:1 hexane ethyl acetate mixtures as the eluent. Fractions containingthe desired material were grouped and concentrated to provide a yellowcolored oil (6.91 g). NMR analysis of the yellow colored oil confirmedthat the structure was consistent with7,7-dimethyl-3-trifluoromethyl-10-vinyl-7H-benzo[c]fluoren-5-ol.

Example 20A

The procedure from Example 5A was followed except that1-(4-fluorophenyl)-1-(4-butoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol and the productfrom Example 20 was used in place of8,10-dibromo-7,7-dimethyl-3-(trifluoromethyl)-7H-benzo[c]fluoren-5-ol.NMR analysis of the foam indicated a structure that was consistent with3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-vinyl-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 21

Step 1

The product from Step 1 of Example 20,7,7-dimethyl-3-(trifluoronnethyl)-10-vinyl-7H-benzo[c]fluorenol-5-ol(5.87 g) was dissolved in dichloromethane (20 mL). Triethylamine (7 mL)was added and stirred for 5 mins. Triisopropylsilyltrifloromethanesulfonate (11.00 g) was added drop-wise. The reactionmixture was stirred at room temperature for 30 min. Saturated sodiumbicarbonate (300 mL) was poured into the reaction mixture and stirredfor 5 min. The aqueous was diluted with dichloromethane and partitioned.The organic layer was collected, dried with anhydrous sodium sulfate andfiltered. The filtrate was concentrated to provide a residue. Theresidue was purified by column chromatography using activated aluminabasic and 9:1 hexane ethyl acetate mixtures as the eluent. Fractionscontaining the desired material were grouped and concentrated to providea colorless oil (6.91 g).

Step 2

The product from Step 1 of Example 21 (6.91 g) was dissolved int-butanol (42 mL), water (94 mL) and cooled to 0° C. A solution of KMNO4(6.4 g) in water (60 mL) was added slowly to the solution of thestarting material. The pH of the solution was adjusted to 8-10 by theaddition of aqueous sodium carbonate. The ice bath was removed and thereaction mixture was warmed to room temperature and stirred for 20 h.The mixture was filtered through a bed of Celite and the filtrate wascarefully acidified to pH 4 by the addition of 10% aqueous HCl. Theaqueous solution was partitioned with ethyl acetate and the organiclayer was collected, dried with anhydrous sodium sulfate andconcentrated in vacuo to afford an oily residue. The oily residue waspurified through a silica plug and eluted with 4:1 hexane ethyl acetatemixtures. Fractions containing the desired material were grouped andconcentrated in vacuo to provide a white solid (3.36 g). NMR analysis ofthe white solid indicated a structure that was consistent with7,7-dimethyl-3-(trifluoromethyl)-5-((triisopropylsilypoxy)-7H-benzo[c]fluorene-10-carboxylicacid.

Step 3

The product from Step 2 of Example 21 (1.80 g) was dissolved inmethylene chloride (10 mL). Methanol (0.2 mL) was added followed bydimethylamino pyridine (0.06 g) and N,N′-dicylcohexylcabodiimide (0.85g). The mixture was stirred for 1 h at room temperature. The mixture wasdiluted with methylene chloride and filtered. The filtrate was collectedand concentrated in vacuo. The crude material was dissolved in THF (12mL) and water (12 mL). Potassium fluoride (0.6 g) was added and themixture stirred at room temperature for 18 h. Ethyl acetate (100 mL) wasadded and was partitioned with water. The ethyl acetate extract wascollected, dried with anhydrous sodium sulfate and concentrated in vacuoto provide a residue. The residue was dissolved in methylene chlorideand hexane was added until a precipitate formed. The precipitate (1.13g) was collected by vacuum filtration and washed with cold hexane. NMRanalysis of the precipitate indicated a structure that was consistentwith7,7-dimethyl-3-trifluoromethyl-10-methoxycarbonyl-7H-benzo[c]fluoren-5-ol.

Example 21A

The procedure from Example 5A was followed except that1-(4-fluorophenyl)-1-(4-butoxyphenyl)prop-2-yn-1-ol was used in place of1-(4-butoxyphenyl)-1-(4-methoxyphenyl)prop-2-yn-1-ol and the productfrom Example 21 was used in place of8,10-dibromo-7,7-dimethyl-3-(trifluoronnethyl)-7H-benzo[c]fluoren-5-ol.NMR analysis of the cream colored solid indicated a structure that wasconsistent with3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-methoxycarbonyl-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 22A

The product from Step 1 of Example 21A (0.63 g) was dissolved intetrahydrofuran (10 mL), methanol (5 mL). 50% wt aqueous sodiumhydroxide (3 mL) was added and the mixture was stirred at roomtemperature for 30 min. The mixture was poured in 10% aqueous HCl andstirred for 5 min. The aqueous was partitioned with ethyl acetate. Theethyl acetate layer was collected, dried with anhydrous sodium sulfateand concentrated to provide a residue. The residue was purified bycolumn chromatography using 4:1 hexanes ethyl acetate mixtures.Fractions containing the desired material were grouped and concentratedto provide a purple colored foam (0.56 g). NMR analysis of the purplecolored foam indicated a structure that was consistent with3-(4-fluorophenyl)-3-(4-butoxyphenyl)-10-(carboxylicacid)-6-trifluoromethyl-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 23

The product from Step 2 of Example 21 (0.51 g) and4′-(trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4-amine (0.31 g) weredissolved in DCM (10 mL). DMAP (0.10 g) and DBSA (0.05 g) was addedfollowed by DCC (0.25 g). The reaction mixture was stirred at roomtemperature for 2 h. The reaction mixture was filtered through a silicaplug and the filtrate was collected and concentrated. The residue wasdissolved in THF (10 mL) and a solution of potassium fluoride (0.6 g) inwater (5 mL) was added and stirred at room temperature for 18 h. Thereaction mixture was diluted with EtOAc and partitioned. The EtOAc layerwas collected and concentrated to provide a residue. The residue waspurified by column chromatography using 4:1 hexanes ethyl acetatemixtures. Fractions containing the desired material were grouped andconcentrated to provide a white solid (0.47 g). NMR analysis of thewhite solid indicated a structure that was consistent with7,7-dimethyl-3-trifluoromethyl-10-[(4′-(trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4-yl)carbamoyl]-7H-benzo[c]fluoren-5-ol.

Example 24

The procedure from Example 23 was followed except that4′-(trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4-ol was used in place of4′-(trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4-amine. NMR analysis ofthe white solid indicated a structure that was consistent with7,7-dimethyl-3-trifluoromethyl-10-[((4′-(trans-4-pentylcyclohexyl)-[1,1′-biphenyl]-4-yl)oxy)carbonyl]-7H-benzo[c]fluoren-5-ol.

Example 25

Procedures from Steps 1 to 4 of Example 5 were followed except that inStep 1, 3,5-dichlorobromobenzene and 4-methoxybenzoyl chloride was usedin place of tribromobenzene and 4-trifluoromethylbenzoyl chloride.Compound 2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ylacetate was obtained as the undesired major product. The desired minorproduct was also collected as off-white powder. NMR indicated that thedesired product had a structure consistent with10-acetyl-2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ylacetate. The formation of more of the desired minor product could beachieved by extending the reaction time in Step 4.

Example 26

A mixture of10-acetyl-2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluoren-5-ylacetate from Example 25 (3.5 g), 3-Chloroperoxybenzoic acid (4 g) anddichloromethane were placed in a reaction flask and refluxed for 4hours. The reaction mixture was stirred at room temperature for 17hours. All solvent was removed. Methanol (100 ml) was added to theobtained solid and the mixture was stirred at room temperature for 10minutes. Solid was collected by vacuum filtration and further purifiedby recrystallization from mixture solvent dichloromethane and methanol.White crystals (3.4 g) were obtained as the product. NMR indicated thatthe product had a structure consistent with2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluorene-5,10-diyldiacetate.

Example 27

To a stirred mixture of2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluorene-5,10-diyldiacetate (3.4 g) from Example 24 and THF (100 ml), 50 wt % watersolution of sodium hydroxide (10 ml) was added. The mixture was refluxedfor 10 minutes. Ethyl acetate (100 ml) was then added and pH of themixture was adjusted to 2 using 3 N HCl water solution. The mixture wasextracted with water, dried over magnesium sulfate and concentrated.Yellow oil (1.9 g) was obtained as the product. NMR indicated that theproduct had a structure consistent with2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluorene-5,10-diol.

Example 27A

A mixture of2,4-dichloro-9-methoxy-7,7-dimethyl-7H-benzo[c]fluorene-5,10-diol fromExample 27 (1.9 g), 1,1-bis(4-methoxyphenyl)prop-2-yn-1-ol (1.3 g),p-toluenesulfonic acid (0.1 g) and methylene chloride (100 ml) wasrefluxed for an hour. All solvent was removed. The black crude productwas purified using a CombiFlash followed by recrystallization frommethylene chloride/methanol. Yellow crystals (0.9 g) were obtained asthe product. NMR indicated the minor product had a structure consistentwith3,3-bis(4-methoxyphenyl)-5,7-dichloro-10-hydroxy-11-methoxy-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Example 28A

To a stirred mixture of3,3-bis(4-methoxyphenyl)-5,7-dichloro-10-hydroxy-11-methoxy-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyranfrom Example 27A (0.3 g), methylene chloride (50 ml) and triethylamine(2 ml), methylene chloride (10 ml) solution of trifluoromethanesulfonicanhydride (1 g) was dropped in slowly in 5 minutes. After the addition,the mixture was stirred at room temperature for 5 minutes and then waterwas added (50 ml). The organic layer was collected, washed withHCl/water (1 mol/L, 50 ml) washed with saturated sodium bicarbonatewater solution (50 ml), dried over magnesium sulfate and concentrated.The crude product was plug-columned over silica gel using toluene assolvent. After evaporation of solvent, product was purified byrecrystallization from methylene chloride/methanol. Yellow crystals (0.2g) were obtained as the product. NMR indicated the minor product had astructure consistent with3,3-bis(4-methoxyphenyl)-5,7-dichloro-10-trifluoromethanesulfonyl-11-methoxy-13,13-dimethyl-3,13-dihydro-indeno[2′,3′:3,4]naphtho[1,2-b]pyran.

Part 2 Photochromic Property Testing

Part 2A—Test Square Preparation

Testing was done with the compounds described in Examples 2A-5A, 9A,10A, 13A, 18A-22A, 27A and 28A in the following manner. A quantity ofcompound calculated to yield a 1.5×10⁻³ molal solution was added to aflask containing 50 grams of a monomer blend of 4 parts ethoxylatedbisphenol A dimethacrylate (BPA 2EO DMA), 1 part poly(ethylene glycol)600 dimethacrylate, and 0.033 weight percent 2,2′-azobis(2-methylpropionitrile) (AlBN). Each compound was dissolved into the monomerblend by stirring and gentle heating, if necessary. After a clearsolution was obtained, the sample was degassed in a vacuum oven for 5-10minutes at 25 torr. Using a syringe, the sample was poured into a flatsheet mold having an interior dimension of 2.2 mm+/−0.3 mm×6 inch (15.24cm)×6 inch (15.24 cm). The mold was sealed and placed in a horizontalairflow, programmable oven to ramp from 40° C. to 95° C. over a 5 hourinterval, hold the temperature at 95° C. for 3 hours, ramp down to 60°C. over a 2 hour interval and then hold at 60° C. for 16 hours. Aftercuring, the mold was opened, and the polymer sheet was cut into 2 inch(5.1 cm) test squares using a diamond blade saw.

Part 2B—Response Testing

Prior to response testing on the optical bench, the photochromic testsquares from Part 2A were conditioned by exposure to 365 nm ultravioletlight for about 30 minutes at a distance of about 14 cm from the sourceto cause the photochromic material to transform from the groundstate-form to an activated-state form, and then placed in a 75° C. ovenfor about 20 minutes to allow the photochromic material to revert backto the ground state-form. The test squares were then cooled to roomtemperature, exposed to fluorescent room lighting for at least 2 hours,and then kept covered (that is, in a dark environment) for at least 2hours prior to testing on an optical bench.

The optical bench was fitted with an Newport Model #67005 300-watt Xenonarc lamp, and Model 69911 power supply, Vincent Associates (modelVS25S2ZM0R3 with VMM-D4 controller) high-speed computer controlledshutter, a Schott 3 mm KG-2 band-pass filter, which removed shortwavelength radiation, neutral density filter(s) to attenuate light fromthe xenon lamp, a fused silica condensing lens for beam collimation, anda fused silica water cell/sample holder for maintaining sampletemperature in which the test sample to be tested was inserted. Thetemperature in the water cell was controlled with a pumped watercirculation system in which the water passed through copper coils thatwere placed in the reservoir of a chiller unit. The water cell used tohold test samples contained fused silica sheets on the front and backfacings in order to eliminate spectral change of the activation ormonitoring light beams. The filtered water passing through the watercell was maintained at 73.4° F.±2° (23° C.±1.1°) for photochromicresponse testing. A Newport Model 689456 Digital Exposure Timer was usedto control the intensity of the xenon arc lamp during activation of thesample.

A custom broadband tungsten lamp based light source for monitoringresponse measurements was positioned in a perpendicular manner to asurface of the cell assembly. After passing through the sample, thelight was refocused into a 2-inch integrating sphere and fed to an OceanOptics S2000 spectrophotometer by fiber optic cables. Ocean OpticsSpectraSuite and PPG proprietary software were used to measure responseand control the operation of the optical bench.

Irradiance for response testing of the samples on the optical bench wasestablished at the sample surface using an International Light ResearchRadiometer, Model IL-1700 with a detector system comprising a ModelSED033 detector, B Filter and diffuser. The output display of theradiometer was corrected (factor values set) against a Licor 1800-02Optical Calibration Calibrator in order to display values representingWatts per square meter UVA. The irradiance at the sample point forinitial response testing was set at to 3.0 Watts per square meter UVAand approximately 8.6 Klux illuminance. During sample response testing,if a sample darkened beyond an acceptable detection capability limit,the irradiance was lowered to 1.0 Watts per square meter UVA or thesample was remade at a one-half concentration in the copolymer.

Adjusting the output of the filtered xenon arc lamp was accomplished byincreasing or decreasing the current to the lamp through the controllerand/or by adding or removing neutral density filters in the light path.The test samples were exposed to the activation light at 31° normal toits surface while being perpendicular to the monitoring light.

Samples were activated in the 73.4° F. (23° C.) controlled water cellfor 30 minutes, then allowed to fade under room light conditions untilthe change in optical density of the activated sample faded to ¼ of itshighest dark (saturated) state or for a maximum of 30 minutes of fade.

Change in optical density (ΔOD) from the bleached state to the darkenedstate was determined by establishing the initial transmittance, openingthe shutter from the Xenon lamp to provide ultraviolet radiation tochange the test lens from the bleached state to an activated (i.e.,darkened) state. Data was collected at selected intervals of time,measuring the transmittance in the activated state, and calculating thechange in optical density according to the formula: ΔOD=log(% Tb/% Ta),where % Tb is the percent transmittance in the bleached state, % Ta isthe percent transmittance in the activated state and the logarithm is tothe base 10.

The λ_(max-vis) in the visible light range is the wavelength in thevisible spectrum at which the maximum absorption of the activated formof the photochromic compound occurs. The λ_(max-vis) was determined bytesting the photochromic test square in a Varian Cary 4000 UV-Visiblespectrophotometer or comparable equipment.

The ΔOD/Min, which represents the sensitivity of the photochromiccompound's response to UV light, was measured over the first five (5)seconds of UV exposure, then expressed on a per minute basis. Thesaturation optical density (ΔOD at saturation) was taken under identicalconditions except UV exposure was continued for a total of 30 minutes.The fade half life is the time interval in seconds for the ΔOD of theactivated form of the photochromic compound in the test squares to reachone half the ΔOD measured after thirty minutes, or after saturation ornear-saturation was achieved, at room temperature after removal of thesource of activating light, e.g., by closing the shutter. Results arelisted in Table I.

TABLE 1 Photochromic Performance Test Results Sensitivity ΔOD at Example# λ_(max-vis) (nm) (ΔOD/Min) saturation T½ (sec)  2A 572 0.44 0.27 35 3A 564 0.46 0.34 44  4A 551 0.65 0.44 35  5A 565 0.23 0.09 14  9A 6030.33 0.18 28 10A 562 0.28 0.10 14 13A 572 0.26 0.26 93 18A 550 0.49 0.3639 19A 555 0.17 0.20 176 20A 563 0.22 0.36 224 21A 556 0.40 0.29 35 22A557 0.43 0.30 35 27A 588 1.07 0.88 79 28A 572 0.91 0.53 34

The present invention has been described with reference to specificdetails of particular embodiments thereof. It is not intended that suchdetails be regarded as limitations upon the scope of the inventionexcept insofar as to the extent that they are included in theaccompanying claims.

We claim:
 1. An indeno-fused ring compound represented by the followingFormula I,

wherein, (A) Ring-A is selected from unsubstituted aryl, substitutedaryl, unsubstituted fused ring aryl, or substituted fused ring aryl, (B)Q′ is selected from halogen, —OH, —N₃, —NR^(a)R^(a), —N(R^(a))C(O)Q″,—CN, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)),—OC(O)R^(a), —OC(O)OR^(a), —SR^(a), —OS(O₂)R^(b), —C(O)NR^(a)R^(a) and alengthening agent L, wherein each R^(a) is independently selected fromhydrogen, hydrocarbyl and substituted hydrocarbyl each optionally andindependently interrupted with at least one of —O—, —S—, —C(O)—,—C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₁₄)_(u)(R₁₄)_(v)—, where u and v are each independently selectedfrom 0 to 2, provided that the sum of u and v is 2, and each R₁₄ isindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and combinations of two or more thereof, or two R^(a)groups come together with —N and optionally an additional hetero atomselected from N and O to form a heterocycloalkyl, and R^(b) is selectedfrom perhalohydrocarbyl, and Q″ is selected from halo, —OR^(a),—NR^(a)R^(a), —C(O)OR^(a), —SR^(a), and hydrocarbyl or substitutedhydrocarbyl, wherein said substituents are selected from —OH,—NR^(a)R^(a), —C(O)OR^(a), —SR^(a), wherein said lengthening agent L isrepresented by the following formula,—(S₁)_(c)-(Q₁-(S₂)_(d))_(d′)-(Q₂-(S₃)_(e))_(e′)-(Q₃-(S₄)_(f))_(f′)-S₅-Pwherein, (i) each Q₁, Q₂, and Q₃ is independently chosen for eachoccurrence from, a divalent group chosen from, an unsubstituted or asubstituted aromatic group, an unsubstituted or a substituted alicyclicgroup, an unsubstituted or a substituted heterocyclic group, andmixtures thereof, wherein substituents are chosen from, a grouprepresented by P, liquid crystal mesogens, halogen, poly(C₁-C₁₈ alkoxy),C₁-C₁₈ alkoxycarbonyl, C₁-C₁₈ alkylcarbonyl, C₁-C₁₈ alkoxycarbonyloxy,aryloxycarbonyloxy, perfluoro(C₁-C₁₈)alkoxy,perfluoro(C₁-C₁₈)alkoxycarbonyl, perfluoro(C₁-C₁₈)alkylcarbonyl,perfluoro(C₁-C₁₈)alkylamino, di-(perfluoro(C₁-C₁₈)alkyl)amino,perfluoro(C₁-C₁₈)alkylthio, C₁-C₁₈ alkylthio, C₁-C₁₈ acetyl, C₃-C₁₀cycloalkyl, C₃-C₁₀ cycloalkoxy, a straight-chain or branched C₁-C₁₈alkyl group that is mono-substituted with cyano, halo, or C₁-C₁₈ alkoxy,or poly-substituted with halo, and a group comprising one of thefollowing formulae: -M(T)_((t-1)) and -M(OT)_((t-1)), wherein M ischosen from aluminum, antimony, tantalum, titanium, zirconium andsilicon, T is chosen from organofunctional radicals, organofunctionalhydrocarbon radicals, aliphatic hydrocarbon radicals and aromatichydrocarbon radicals, and t is the valence of M, (ii) c, d, e, and f areeach independently chosen from an integer ranging from 0 to 20,inclusive; and each S₁, S₂, S₃, S₄, and S₅ is independently chosen foreach occurrence from a spacer unit chosen from: (1) optionallysubstituted alkylene, optionally substituted haloalkylene,—Si(Z′)₂(CH₂)_(g)—, and

 wherein each Z′ is independently selected from hydrogen, C₁-C₁₈ alkyl,C₃-C₁₀ cycloalkyl, and aryl; g for each occurrence is independentlychosen from an integer from 1 to 20; h for each occurrence isindependently chosen from an integer from 1 to 16; and said substituentsfor the alkylene and haloalkylene are independently selected from C₁-C₁₈alkyl, C₃-C₁₀ cycloalkyl and aryl; (2) —N(Z)—, —C(Z)═C(Z)—, —C(Z)═N—,—C(Z′)₂—C(Z′)₂—, or a single bond, wherein Z is independently chosen foreach occurrence from hydrogen, C₁-C₈ alkyl, C₃-C₁₀ cycloalkyl and aryl,and Z′ is independently chosen for each occurrence from C₁-C₁₈ alkyl,C₃-C₁₀ cycloalkyl and aryl; and (3) —O—, —C(O)—, —C≡C—, —N═N—, —S—,—S(O)—, —S(O)(O)—, —(O)S(O)—, —(O)S(O)O—, —O(O)S(O)O—, or straight-chainor branched C₁-C₂₄ alkylene residue, said C₁-C₂₄ alkylene residue beingunsubstituted, mono-substituted by cyano or halo, or poly-substituted byhalo, provided that when two spacer units comprising heteroatoms arelinked together the spacer units are linked so that heteroatoms are notdirectly linked to each other, and provided that when S₁ and S₅ arelinked to Formula I and P, respectively, they are linked so that twoheteroatoms are not directly linked to each other, (iii) P is chosenfrom: hydroxy, amino, C₂-C₁₈ alkenyl, C₂-C₁₈ alkynyl, azido, silyl,siloxy, silylhydride, (tetrahydro-2H-pyran-2-yl)oxy, thio, isocyanato,thioisocyanato, acryloyloxy, methacryloyloxy,2-(acryloyloxy)ethylcarbamyl, 2-(methacryloyloxy)ethylcarbamyl,aziridinyl, allyloxycarbonyloxy, epoxy, carboxylic acid, carboxylicester, acryloylamino, methacryloylamino, aminocarbonyl, C₁-C₁₈ alkylaminocarbonyl, aminocarbonyl(C₁-C₁₈)alkyl, C₁-C₁₈ alkyloxycarbonyloxy,halocarbonyl, hydrogen, aryl, hydroxy(C₁-C₁₈)alkyl, C₁-C₁₈ alkyl, C₁-C₁₈alkoxy, amino(C₁-C₁₈)alkyl, C₁-C₁₈ alkylamino, di-(C₁-C₁₈)alkylamino,C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, C₁-C₁₈ alkoxy(C₁-C₁₈)alkoxy, nitro,poly(C₁-C₁₈)alkyl ether, (C₁-C₁₈)alkyl(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl,polyethyleneoxy, polypropyleneoxy, ethylenyl, acryloyl,acryloyloxy(C₁-C₁₈)alkyl, methacryloyl, methacryloyloxy(C₁-C₁₈)alkyl,2-chloroacryloyl, 2-phenylacryloyl, acryloyloxyphenyl,2-chloroacryloylamino, 2-phenylacryloylaminocarbonyl, oxetanyl,glycidyl, cyano, isocyanato(C₁-C₁₈)alkyl, itaconic acid ester, vinylether, vinyl ester, a styrene derivative, main-chain and side-chainliquid crystal polymers, siloxane derivatives, ethyleneiminederivatives, maleic acid derivatives, fumaric acid derivatives,unsubstituted cinnamic acid derivatives, cinnamic acid derivatives thatare substituted with at least one of methyl, methoxy, cyano and halogen,or substituted or unsubstituted chiral or non-chiral monovalent ordivalent groups chosen from steroid radicals, terpenoid radicals,alkaloid radicals and mixtures thereof, wherein the substituents areindependently chosen from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, amino, C₃-C₁₀cycloalkyl, C₁-C₁₈ alkyl(C₁-C₁₈)alkoxy, fluoro(C₁-C₁₈)alkyl, cyano,cyano(C₁-C₁₈)alkyl, cyano(C₁-C₁₈)alkoxy or mixtures thereof, or P is astructure having from 2 to 4 reactive groups or P is an unsubstituted orsubstituted ring opening metathesis polymerization precursor; and (iv)d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4,provided that a sum of d′+e′+f′ is at least 1; (C) i is selected from 0to 3, t is selected from 0 to a total number of positions to which R²can be bonded, and R¹ for each i, and R² for each t, are eachindependently selected from, hydrocarbyl and substituted hydrocarbyleach optionally and independently interrupted with at least one of —O—,—S—, —C(O)—, —C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)— where R₁₁′ isselected from hydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₁₄)_(u)(R₁₄)_(v)—, where u and v are each independently selectedfrom 0 to 2, provided that the sum of u and v is 2, and each R₁₄ isindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and combinations of two or more thereof; halogen; cyano;and —N(R₁₁′)R₁₂′, wherein R₁₁′ and R₁₂′ are each independently selectedfrom hydrogen, hydrocarbyl or substituted hydrocarbyl, or R₁₁′ and R₁₂′together form a ring structure optionally including at least oneheteroatom, (D) R³ and R⁴ are each independently selected from,hydrogen; hydrocarbyl and substituted hydrocarbyl each optionally andindependently interrupted with at least one of —O—, —S—, —C(O)—,—C(O)O—, —S(O)—, —S(O₂)—, —N═N—, —N(R₁₁′)— where R₁₁′ is selected fromhydrogen, hydrocarbyl or substituted hydrocarbyl,—Si(OR₄)_(u)(R₁₄)_(v)—, where u and v are each independently selectedfrom 0 to 2, provided that the sum of u and v is 2, and each R₁₄ isindependently selected from hydrogen, hydrocarbyl and substitutedhydrocarbyl, and combinations of two or more thereof; or R³ and R⁴together form a ring structure optionally including at least oneheteroatom, and (E) R⁵ is selected from hydrogen, —C(O)—R¹³ or —S(O₂)R¹³wherein R¹³ is hydrocarbyl, or halohydrocarbyl.
 2. The indeno-fused ringcompound of claim 1, wherein, (A) Ring-A is unsubstituted aryl orsubstituted aryl; (B) Q′ is selected from bromo, fluoro, chloro, —N₃,—NR^(a)R^(a), —N(R^(a))C(O)Q″, —C(O)OR^(a), —C(O)R^(a), —C≡C—R^(a),—C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a), —SR^(a),—OS(O₂)R^(b), —C(O)NR^(a)R^(a), and said lengthening agent L, whereineach R′ is independently selected from hydrogen, an unsubstituted orsubstituted alkyl group having from 1 to 18 carbon atoms, anunsubstituted or substituted aryl group, an unsubstituted or substitutedalkene or alkyne group having from 2 to 18 carbon atoms, wherein saidsubstituents are chosen from halo and hydroxyl, or two R^(a) groups cometogether with —N and an additional hetero atom selected from N and O toform a heterocycloalkyl and R^(b) is selected from a perfluorinatedalkyl group having from 1 to 18 carbon atoms, and Q″ is selected from—OR^(a), —NR^(a)R^(a), —C(O)OR^(a), —SR^(a), and hydrocarbyl orsubstituted hydrocarbyl, wherein said substituents are selected from—OH, —NR^(a)R^(a), —C(O)OR^(a), —SR^(a), and for lengthening agent L,d′, e′ and f′ are each independently chosen from 0, 1, 2, 3, and 4,provided that a sum of d′+e′+f′ is at least 2; (C) R¹ for each i, and R²for each t, are each independently selected from, (a) —C(O)X₂₄, whereinX₂₄ is chosen from said lengthening agent L, hydroxy, C₁-C₁₈ alkyl,C₁-C₁₈ alkoxy, phenyl that is unsubstituted or mono-substituted withC₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, amino that is unsubstituted, mono- ordi-substituted with at least one of C₁-C₁₈ alkyl, phenyl, benzyl, andnaphthyl, (b) —OX₇ and —N(X₇)₂; wherein X₇ is chosen from: (i) hydrogen,a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ acyl, phenyl(C₁-C₁₈)alkyl,mono(C₁-C₁₈)alkyl substituted phenyl(C₁-C₁₈)alkyl, mono(C₁-C₁₈)alkoxysubstituted phenyl(C₁-C₁₈)alkyl; C₁-C₁₈ alkoxy(C₁-C₁₈)alkyl; C₃-C₁₀cycloalkyl; mono(C₁-C₁₈)alkyl substituted C₃-C₁₀ cycloalkyl, C₁-C₁₈haloalkyl, allyl, benzoyl, mono-substituted benzoyl, naphthoyl ormono-substituted naphthoyl, wherein each of said benzoyl and naphthoylsubstituents are independently chosen from C₁-C₁₈ alkyl, and C₁-C₁₈alkoxy, (ii) —CH(X₈)X₉, wherein X₈ is chosen from hydrogen, alengthening agent L, or C₁-C₁₈ alkyl, and X₉ is chosen from alengthening agent L, —CN, —CF₃, or —COOX₁₀, wherein X₁₀ is chosen fromhydrogen, a lengthening agent L, or C₁-C₁₈ alkyl, (iii) —C(O)X₆, whereinX₆ is chosen from at least one of, hydrogen, a lengthening agent L,C₁-C₁₈ alkoxy, phenoxy that is unsubstituted, mono- or di-substitutedwith C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an aryl group that is unsubstituted,mono- or di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, an aminogroup that is unsubstituted, mono- or di-substituted with C₁-C₁₈ alkyl,and a phenylamino group that is unsubstituted, mono- or di-substitutedwith C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy, or (iv) tri(C₁-C₁₈)alkylsilyl,tri(C₁-C₁₈)alkylsilyloxy, tri(C₁-C₁₈)alkoxysilyl,tri(C₁-C₁₈)alkoxysilyloxy, di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyl,di(C₁-C₁₈)alkyl(C₁-C₁₈ alkoxy)silyloxy, di(C₁-C₁₈)alkoxy(C₁-C₁₈alkyl)silyl or di(C₁-C₁₈)alkoxy(C₁-C₁₈ alkyl)silyloxy; (c) —SX₁₁,wherein X₁₁ is chosen from hydrogen, a lengthening agent L, C₁-C₁₈alkyl, C₁-C₁₈ haloalkyl, an aryl group that is unsubstituted, or mono-or di-substituted with C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, or halogen; (d) anitrogen containing ring represented by Formula i:

wherein, each —Y— is independently chosen for each occurrence from—CH₂—, —CH(R₁₃′)—, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and—C(R₁₃′)(aryl)-, and Z is —Y—, —O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′)—,or —N(aryl)-, wherein each R₁₃′ is independently a lengthening group L,or C₁-C₂₀ alkyl, each aryl is independently phenyl or naphthyl, m is aninteger 1, 2 or 3, and p is an integer 0, 1, 2, or 3, provided that whenp is 0, Z is —Y—; (e) a group represented by Formula ii or iii,

 wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each occurrencefrom hydrogen, a lengthening agent L, C₁-C₁₈ alkyl, phenyl or naphthyl,or X₁₄ and X₁₅ together form a ring of 5 to 8 carbon atoms, p is aninteger chosen from 0, 1, or 2, and X₁₇ is independently chosen for eachoccurrence from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, orhalogen; (f) immediately adjacent R¹ groups, and immediately adjacent R²groups, in each case independently together form a group represented byFormula vii, viii, or ix,

 wherein, (i) W and W′ are independently chosen for each occurrence from—O—, —N(X₇)—, —C(X₁₄)—, and —C(Xr₁₇)—, (ii) wherein X₁₄ and X₁₅ areindependently chosen for each occurrence from hydrogen, a lengtheningagent L, C₁-C₁₈ alkyl, phenyl or naphthyl, or X₁₄ and X₁₅ together forma ring of 5 to 8 carbon atoms; and X₁₇ is independently chosen for eachoccurrence from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, orhalogen, and (iii) q is an integer chosen from 0, 1, 2, 3, and 4; (g)lengthening agent L; (h) a group B selected from, (i) hydrogen, C₁-C₁₈alkyl, C₂-C₁₈ alkylidene, C₂-C₁₈ alkylidyne, vinyl, C₃-C₁₀ cycloalkyl,C₁-C₁₈ haloalkyl, allyl, halogen, and benzyl that is unsubstituted ormono-substituted with at least one of C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy;(ii) phenyl that is mono-substituted at the para position with at leastone substituent chosen from: C₁-C₁₈ alkoxy, linear or branched chainC₁-C₂₀ alkylene, linear or branched chain C₁-C₄ polyoxyalkylene, cyclicC₃-C₂₀ alkylene, phenylene, naphthylene, C₁-C₁₈ alkyl substitutedphenylene, mono- or poly-urethane(C₁-C₂₀)alkylene, mono- orpoly-ester(C₁-C₂₀)alkylene, mono- or poly-carbonate(C₁-C₂₀)alkylene,polysilanylene, polysiloxanylene and mixtures thereof, wherein the atleast one substituent is connected to an aryl group of a photochromicmaterial, (iii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from atleast one of hydrogen, a lengthening agent L, C₁-C₁₈ alkyl that isunsubstituted or mono-substituted with phenyl, phenyl(C₁-C₁₈)alkyl thatis mono-substituted with C₁-C₁₈ alkyl, C₁-C₁₈ haloalkyl or C₁-C₁₈alkoxy, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy, and lengthening agent L, (iv)—CH(X₂)(X₃), wherein, (1) X₂ is chosen from at least one of hydrogen, alengthening agent L, C₁-C₁₈ alkyl, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy; and (2) X₃ ischosen from at least one of —COOX₁, —COX₁, —COX₄, and —CH₂OX₅, wherein,X₄ is chosen from at least one of morpholino, piperidino, amino that isunsubstituted, mono- or di-substituted with C₁-C₁₈ alkyl, and anunsubstituted, mono- or di-substituted group chosen from phenylamino anddiphenylamino, wherein each substituent is independently chosen fromC₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; and X₅ is chosen from hydrogen, alengthening agent L, —C(O)X₂, C₁-C₁₈ alkyl that is unsubstituted ormono-substituted with (C₁-C₁₈)alkoxy or phenyl, phenyl(C₁-C₁₈)alkyl thatis mono-substituted with (C₁-C₁₈)alkoxy, and an aryl group that isunsubstituted, mono- or di-substituted, wherein each aryl substituent isindependently chosen from C₁-C₁₈ alkyl and C₁-C₁₈ alkoxy; (v) anunsubstituted, mono-, di-, or tri-substituted aryl group; 9-julolidinyl;or an unsubstituted, mono- or di-substituted heteroaromatic group chosenfrom pyridyl, furanyl, benzofuran-2-yl, benzofuran-3-yl, thienyl,benzothien-2-yl, benzothien-3-yl, dibenzofuranyl, dibenzothienyl,carbazoyl, benzopyridyl, indolinyl, or fluorenyl; wherein each aryl andheteroaromatic group substituent is independently chosen for eachoccurrence from: (1) lengthening agent L, (2) —COOX₁ or —C(O)X₆; (3)aryl, halogen, haloaryl, C₃-C₁₀ cycloalkylaryl, and an aryl group thatis mono- or di-substituted with C₁-C₁₈ alkyl or C₁-C₁₈ alkoxy; (4)C₁-C₁₈ alkyl, C₃-C₁₀ cycloalkyl, C₃-C₁₀ cycloalkyloxy(C₁-C₁₈)alkyl,aryl(C₁-C₁₈)alkyl, aryloxy(C₁-C₁₈)alkyl, mono- ordi-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkyl, mono- ordi-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkyl, C₁-C₁₈ haloalkyl, andmono(C₁-C₁₈)alkoxy(C₁-C₁₈)alkyl; (5) C₁-C₁₈ alkoxy, C₃-C₁₀ cycloalkoxy,cycloalkyloxy(C₁-C₁₈)alkoxy, aryl(C₁-C₁₈)alkoxy, aryloxy(C₁-C₁₈)alkoxy,mono- or di-(C₁-C₁₈)alkylaryl(C₁-C₁₈)alkoxy, and mono- ordi-(C₁-C₁₈)alkoxyaryl(C₁-C₁₈)alkoxy; (6) aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkylene, amino, mono- or di-alkylamino,diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino,aziridino, indolino, piperidino, morpholino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy,acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂; (8) —SX₁₁; (9)a nitrogen containing ring represented by Formula i; (10) a grouprepresented by Formula ii or iii; (11) an unsubstituted ormono-substituted group chosen from pyrazolyl, imidazolyl, pyrazolinyl,imidazolinyl, pyrrolidinyl, phenothiazinyl, phenoxazinyl, phenazinyl, oracridinyl, wherein each substituent is independently chosen from alengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, phenyl, hydroxy, aminoor halogen; (12) a group represented by Formula iv or v:

wherein, (I) V′ is independently chosen in each formula from —O—, —CH—,C₁-C₆ alkylene, and C₃-C₁₀ cycloalkylene, (II) V is independently chosenin each formula from —O— or —N(X₂₁)—, wherein X₂₁ is hydrogen, alengthening agent L, C₁-C₁₈ alkyl, and C₂-C₁₈ acyl, provided that if Vis —N(X₂₁)—, V′ is —CH₂—, (III) X₁₈ and X₁₉ are each independentlychosen from hydrogen, a lengthening agent L, and C₁-C₁₈ alkyl, and (IV)k is chosen from 0, 1, and 2, and each X₂₀ is independently chosen foreach occurrence from a lengthening agent L, C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy,hydroxy and halogen, and (13) a group represented by Formula vi:

wherein (I) X₂₂ is chosen from hydrogen, a lengthening agent L, andC₁-C₁₈ alkyl, and (II) X₂₃ is chosen from a lengthening agent L and anunsubstituted, mono-, or di-substituted group chosen from naphthyl,phenyl, furanyl and thienyl, wherein each substituent is independentlychosen for each occurrence from C₁-C₁₈ alkyl, C₁-C₁₈ alkoxy, andhalogen; (D) R³ and R⁴ are each independently selected from, (i)hydrogen, C₁-C₂₀ alkyl, C₁-C₂₀ haloalkyl, C₃-C₁₀ cycloalkyl, allyl,benzyl, or mono-substituted benzyl, said benzyl substituents beingchosen from halogen, C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy; (ii) anunsubstituted, mono- di- or tri-substituted group chosen from phenyl,naphthyl, phenanthryl, pyrenyl, quinolyl, isoquinolyl, benzofuranyl,thienyl, benzothienyl, dibenzofuranyl, dibenzothienyl, carbazolyl, orindolyl, said group substituents in each case being independently chosenfrom halogen, C₁-C₂₀ alkyl or C₁-C₂₀ alkoxy; (iii) mono-substitutedphenyl, said substituent located at the para position being —(CH₂)_(t)—or —O—(CH₂)_(t)—, wherein t is the integer 1, 2, 3, 4, 5 or 6, saidsubstituent being connected to an aryl group which is a member of aphotochromic material; (iv) the group —CH(R¹⁰)G, wherein R¹⁰ ishydrogen, C₁-C₂₀ alkyl or the unsubstituted, mono- or di-substitutedaryl groups phenyl or naphthyl, and G is —CH₂OR¹¹, wherein R¹¹ ishydrogen, —C(O)R¹⁰, C₁-C₂₀ alkyl, C₁-C₂₀ alkoxy(C₁-C₂₀)alkyl,phenyl(C₁-C₂₀)alkyl, mono(C₁-C₂₀)alkoxy substituted phenyl(C₁-C₂₀)alkyl,or the unsubstituted, mono- or di-substituted aryl groups phenyl ornaphthyl, each of said phenyl and naphthyl group substituents beingC₁-C₂₀ alkyl or C₁-C₂₀ alkoxy; or (v) R³ and R⁴ together form a spirosubstituent selected from a substituted or unsubstitutedspiro-carbocyclic ring containing 3 to 6 carbon atoms, a substituted orunsubstituted spiro-heterocyclic ring containing 1 or 2 oxygen atoms and3 to 6 carbon atoms including the spirocarbon atom, saidspiro-carbocyclic ring and spiro-heterocyclic ring being annellated with0, 1 or 2 benzene rings, said substituents being hydrogen or C₁-C₂₀alkyl; and (E) R⁵ is selected from hydrogen and —C(O)—R¹³.
 3. Theindeno-fused ring compound of claim 1, wherein, (A) Ring-A isunsubstituted aryl or substituted aryl; (B) Q′ is selected from bromo,chloro, —NR^(a)R^(a), —C(O)R^(a), —C(O)OR^(a), and lengthening agent L,wherein each R^(a) is independently selected from hydrogen and an alkylgroup having from 1 to 6 carbon atoms, or two R^(a) groups come togetherwith —N and an additional N atom to form a heterocycloalkyl and R^(b) isselected from a perfluorinated alkyl group having from 1 to 6 carbonatoms, and for lengthening agent L, d′, e′ and f′ are each independentlychosen from 0, 1, 2, 3, and 4, provided that a sum of d′+e′+f′ is atleast 3; (C) R¹ for each i, and R² for each t, are each independentlyselected from, (a) —C(O)X₂₄, wherein X₂₄ is chosen from lengtheningagent L, hydroxy, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, phenyl that isunsubstituted or mono-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy,amino that is unsubstituted, mono- or di-substituted with at least oneof C₁-C₆ alkyl, phenyl, benzyl, and naphthyl; (b) —OX₇ and —N(X₇)₂;wherein X₇ is chosen from, (i) hydrogen, a lengthening agent L, C₁-C₁₂alkyl, C₁-C₁₂ acyl, phenyl(C₁-C₁₂)alkyl, mono(C₁-C₁₂)alkyl substitutedphenyl(C₁-C₁₂)alkyl, mono(C₁-C₁₂)alkoxy substituted phenyl(C₁-C₁₂)alkyl;C₁-C₁₂ alkoxy(C₁-C₁₂)alkyl; C₃-C₇ cycloalkyl; mono(C₁-C₁₂)alkylsubstituted C₃-C₇ cycloalkyl, C₁-C₁₂ haloalkyl, allyl, benzoyl,mono-substituted benzoyl, naphthoyl or mono-substituted naphthoyl,wherein each of said benzoyl and naphthoyl substituents areindependently chosen from C₁-C₆ alkyl, and C₁-C₆ alkoxy; (ii) —CH(X₈)X₉,wherein X₈ is chosen from hydrogen, a lengthening agent L, or C₁-C₁₂alkyl; and X₉ is chosen from a lengthening agent L, —CN, —CF₃, or—COOX₁₀, wherein X₁₀ is chosen from hydrogen, a lengthening agent L, orC₁-C₁₂ alkyl; (iii) —C(O)X₆, wherein X₆ is chosen from at least one of,hydrogen, a lengthening agent L, C₁-C₁₂ alkoxy, phenoxy that isunsubstituted, mono- or di-substituted with C₁-C₁₂ alkyl or C₁-C₁₂alkoxy, an aryl group that is unsubstituted, mono- or di-substitutedwith C₁-C₆ alkyl or C₁-C₆ alkoxy, an amino group that is unsubstituted,mono- or di-substituted with C₁-C₆ alkyl, and a phenylamino group thatis unsubstituted, mono- or di-substituted with C₁-C₆ alkyl or C₁-C₆alkoxy; (c) a nitrogen containing ring represented by Formula i;

wherein, each —Y— is independently chosen for each occurrence from—CH₂—, —CH(R₁₃′)—, —C(R₁₃′)_(r), —CH(aryl)-, —C(aryl)₂-, and—C(R₁₃′)(aryl)-, and Z is —Y—, —O—, —S—, —S(O)—, —SO₂≦, —NH—, —N(R₁₃′)—,or —N(aryl)-, wherein each R₁₃′ is independently a lengthening group L,or C₁-C₂₀ alkyl, each aryl is independently phenyl or naphthyl, m is aninteger 1, 2 or 3, and p is an integer 0, 1, 2, or 3, provided that whenp is 0, Z is —Y—; (d) the group represented by Formula II or iii;

 wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each occurrencefrom hydrogen, a lengthening agent L, C₁-C₁₂ alkyl, phenyl or naphthyl,or X₁₄ and X₁₅ together form a ring of 5 to 7 carbon atoms; p is aninteger chosen from 0, 1, or 2, and X₁₇ is independently chosen for eachoccurrence from a lengthening agent L, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, orhalogen; (e) immediately adjacent R¹ groups, and immediately adjacent R²groups, in each case independently together form a group represented byFormula vii, viii, or ix,

 wherein, (i) W and W′ are independently chosen for each occurrence from—O—, —N(X₇)—, —C(X₁₄)—, and —C(X₁₇)—, (ii) wherein X₁₄ and X₁₅ areindependently chosen for each occurrence from hydrogen, a lengtheningagent L, C₁-C₁₂ alkyl, phenyl or naphthyl, or X₁₄ and X₁₅ together forma ring of 5 to 7 carbon atoms; and X₁₇ is independently chosen for eachoccurrence from a lengthening agent L, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, orhalogen, and (iii) q is an integer chosen from 0 to 3; (f) lengtheningagent L, (g) a group B selected from, (i) C₁-C₁₂ alkyl, C₃-C₇cycloalkyl, C₁-C₁₂ haloalkyl and benzyl that is unsubstituted ormono-substituted with at least one of C₁-C₈ alkyl and C₁-C₆ alkoxy; (ii)—CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen from at least one ofhydrogen, lengthening agent L, C₁-C₁₂ alkyl that is unsubstituted ormono-substituted with phenyl, phenyl(C₁-C₆)alkyl that ismono-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy, and an aryl groupthat is unsubstituted, mono- or di-substituted, wherein each arylsubstituent is independently chosen from C₁-C₆ alkyl and C₁-C₆ alkoxy;and lengthening agent L; (iii) —CH(X₂)(X₃), wherein, (1) X₂ is chosenfrom at least one of lengthening agent L, C₁-C₁₂ alkyl, and an arylgroup that is unsubstituted, mono- or di-substituted, wherein each arylsubstituent is independently chosen from C₁-C₆ alkyl and C₁-C₆ alkoxy;and (2) X₃ is chosen from at least one of —COOX₁, —COX₁, —COX₄, and—CH₂OX₅, wherein: X₄ is chosen from at least one of morpholino,piperidino, amino that is unsubstituted, mono- or di-substituted withC₁-C₆ alkyl, and an unsubstituted, mono or di-substituted group chosenfrom phenylamino and diphenylamino, wherein each substituent isindependently chosen from C₁-C₆ alkyl or C₁-C₆ alkoxy; and X₅ is chosenfrom hydrogen, lengthening agent L, —C(O)X₂, C₁-C₁₂ alkyl that isunsubstituted or mono-substituted with (C₁-C₁₂)alkoxy or phenyl,phenyl(C₁-C₁₂)alkyl that is mono-substituted with (C₁-C₁₂)alkoxy, and anaryl group that is unsubstituted, mono- or di-substituted, wherein eacharyl substituent is independently chosen from C₁-C₆ alkyl and C₁-C₆alkoxy; (iv) an unsubstituted, mono-, di-, or tri-substituted arylgroup; 9-julolidinyl; or an unsubstituted, mono- or di-substitutedheteroaromatic group chosen from pyridyl, furanyl, benzofuran-2-yl,benzofuran-3-yl, thienyl, benzothien-2-yl, benzothien-3-yl,dibenzofuranyl, dibenzothienyl, carbazoyl, benzopyridyl, indolinyl, orfluorenyl; wherein each aryl and heteroaromatic group substituent isindependently chosen for each occurrence from: (1) lengthening agent L;(2) —COOX₁ or —C(O)X₆; (3) aryl, haloaryl, C₃-C₇ cycloalkylaryl, and anaryl group that is mono- or di-substituted with C₁-C₁₂ alkyl or C₁-C₁₂alkoxy; (4) C₁-C₁₂ alkyl, C₃-C₇ cycloalkyl, C₃-C₇cycloalkyloxy(C₁-C₁₂)alkyl, aryl(C₁-C₁₂)alkyl, aryloxy(C₁-C₁₂)alkyl,mono- or di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkyl, mono- ordi-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkyl, haloalkyl, andmono(C₁-C₁₂)alkoxy(C₁-C₁₂)alkyl; (5) C₁-C₁₂ alkoxy, C₃-C₇ cycloalkoxy,cycloalkyloxy(C₁-C₁₂)alkoxy, aryl(C₁-C₁₂)alkoxy, aryloxy(C₁-C₁₂)alkoxy,mono- or di-(C₁-C₁₂)alkylaryl(C₁-C₁₂)alkoxy, and mono- ordi-(C₁-C₁₂)alkoxyaryl(C₁-C₁₂)alkoxy; (6) amido, amino, mono- ordi-alkylamino, diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino,N-arylpiperazino, aziridino, indolino, piperidino, morpholino,thiomorpholino, tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl,hydroxy, acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂; (8)an unsubstituted or mono-substituted group chosen from pyrazolyl,imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl,phenoxazinyl, phenazinyl, or acridinyl, wherein each substituent isindependently chosen from lengthening agent L, C₁-C₈ alkyl, C₁-C₈alkoxy, phenyl, hydroxy, amino or halogen; (D) R³ and R⁴ are eachindependently selected from hydrogen, C₁-C₈ alkyl, C₁-C₈ haloalkyl, andC₃-C₇ cycloalkyl, or R³ and R⁴ together form a spiro substituentselected from a substituted or unsubstituted spiro-carbocyclic ringcontaining 3 to 6 carbon atoms; and (E) R⁵ is selected from hydrogen and—C(O)—R¹³.
 4. The indeno-fused ring compound of claim 1, wherein, (A)Ring-A is unsubstituted aryl or substituted aryl; (B) for Q′, each R^(a)is independently selected from hydrogen and an alkyl group having from 1to 6 carbon atoms, and R^(b) is selected from a perfluorinated alkylgroup having from 1 to 6 carbon atoms; (C) R¹ for each i, and R² foreach t, are each independently selected from, (a) —C(O)X₂₄, wherein X₂₄is chosen from hydroxy, C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl that isunsubstituted or mono-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy,amino that is unsubstituted, mono- or di-substituted with at least oneof C₁-C₆ alkyl, phenyl, benzyl, and naphthyl; (b) —OX₇ and —N(X₇)₂;wherein X₇ is chosen from, (i) hydrogen, C₁-C₆ alkyl, C₁-C₆ acyl,phenyl(C₁-C₆)alkyl, mono(C₁-C₆)alkyl substituted phenyl(C₁-C₆)alkyl,mono(C₁-C₆)alkoxy substituted phenyl(C₁-C₆)alkyl; C₁-C₆alkoxy(C₁-C₆)alkyl; C₃-C₅ cycloalkyl; mono(C₁-C₆)alkyl substituted C₃-C₅cycloalkyl, C₁-C₆ haloalkyl, allyl, benzoyl, mono-substituted benzoyl,naphthoyl or mono-substituted naphthoyl, wherein each of said benzoyland naphthoyl substituents are independently chosen from C₁-C₃ alkyl,and C₁-C₃ alkoxy, (ii) —CH(X₈)X₉, wherein X₈ is chosen from hydrogen orC₁-C₆ alkyl; and X₉ is chosen from —CN, —CF₃, or —COOX₁₀, wherein X₁₀ ischosen from hydrogen or C₁-C₆ alkyl, and (iii) —C(O)X₆, wherein X₆ ischosen from hydrogen, C₁-C₁₂ alkoxy, phenoxy that is unsubstituted,mono- or di-substituted with C₁-C₆ alkyl or C₁-C₆ alkoxy, an aryl groupthat is unsubstituted, mono- or di-substituted with C₁-C₃ alkyl or C₁-C₃alkoxy, an amino group that is unsubstituted, mono- or di-substitutedwith C₁-C₃ alkyl, and a phenylamino group that is unsubstituted, mono-or di-substituted with C₁-C₃ alkyl or C₁-C₃ alkoxy; (c) nitrogencontaining ring represented by Formula i,

 wherein, each —Y— is independently chosen for each occurrence from—CH₂—, —CH(R₁₃′)—, —C(R₁₃′)₂—, —CH(aryl)-, —C(aryl)₂-, and—C(R₁₃′)(aryl)-, and Z is —Y—, —O—, —S—, —S(O)—, —SO₂—, —NH—, —N(R₁₃′)—,or —N(aryl)-, wherein each R₁₃′ is independently lengthening group L, orC₁-C₂₀ alkyl, each aryl is independently phenyl or naphthyl, m is aninteger 1, 2 or 3, and p is an integer 0, 1, 2, or 3, provided that whenp is 0, Z is —Y—; (d) a group represented by Formula ii or iii,

 wherein X₁₄, X₁₅, and X₁₆ are independently chosen for each occurrencefrom hydrogen, C₁-C₆ alkyl, or phenyl or X₁₄ and X₁₅ together form aring of 5 to 7 carbon atoms; p is an integer chosen from 0, 1, or 2, andX₁₇ is independently chosen for each occurrence from C₁-C₆ alkyl, C₁-C₆alkoxy, or halogen; (e) immediately adjacent R¹ groups, and immediatelyadjacent R² groups, in each case independently together form a grouprepresented by Formula vii, viii, or ix,

 wherein, (i) W and W′ are independently chosen for each occurrence from—O—, —N(X₇)—, —C(X₁₄)—, and —C(X₁₇)—, (ii) wherein X₁₄ and X₁₅ areindependently chosen for each occurrence from hydrogen, C₁-C₆ alkyl,phenyl or naphthyl, or X₁₄ and X₁₅ together form a ring of 5 to 7 carbonatoms; and X₁₇ is independently chosen for each occurrence from C₁-C₆alkyl, C₁-C₆ alkoxy, or halogen, and (iii) q is an integer chosen from 0to 3; (f) lengthening agent L, (g) a group B selected from, (i) C₁-C₆alkyl, C₃-C₅ cycloalkyl, C₁-C₆ haloalkyl and benzyl that isunsubstituted or mono-substituted with at least one of C₁-C₃ alkyl andC₁-C₃ alkoxy; (ii) —CH(CN)₂ and —CH(COOX₁)₂, wherein X₁ is chosen fromhydrogen, C₁-C₆ alkyl that is unsubstituted or mono-substituted withphenyl, phenyl(C₁-C₃)alkyl that is mono-substituted with C₁-C₃ alkyl orC₁-C₃ alkoxy, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₃ alkyl and C₁-C₃ alkoxy; and lengthening agent L; (iv)—CH(X₂)(X₃), wherein, (1) X₂ is chosen from at least one of lengtheningagent L, C₁-C₆ alkyl, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₃ alkyl and C₁-C₃ alkoxy; and (2) X₃ is chosen from at leastone of —COOX₁, —COX₁, —COX₄, and —CH₂OX₅, wherein: X₄ is chosen from atleast one of morpholino, piperidino, amino that is unsubstituted, mono-or di-substituted with C₁-C₃ alkyl, and an unsubstituted, mono ordi-substituted group chosen from phenylamino and diphenylamino, whereineach substituent is independently chosen from C₁-C₃ alkyl or C₁-C₃alkoxy; and X₅ is chosen from hydrogen, lengthening agent L, —C(O)X₂,C₁-C₆ alkyl that is unsubstituted or mono-substituted with (C₁-C₆)alkoxyor phenyl, phenyl(C₁-C₁₂)alkyl that is mono-substituted with(C₁-C₆)alkoxy, and an aryl group that is unsubstituted, mono- ordi-substituted, wherein each aryl substituent is independently chosenfrom C₁-C₃ alkyl and C₁-C₃ alkoxy; (v) an unsubstituted, mono-, di-, ortri-substituted aryl group; 9-julolidinyl; or an unsubstituted, mono- ordi-substituted heteroaromatic group chosen from pyridyl, furanyl,benzofuran-2-yl, benzofuran-3-yl, thienyl, benzothien-2-yl,benzothien-3-yl, dibenzofuranyl, dibenzothienyl, carbazoyl,benzopyridyl, indolinyl, or fluorenyl; wherein each substituent isindependently chosen for each occurrence from, (1) lengthening agent L;(2) —C(O)X₆; (3) aryl, haloaryl, C₃-C₇ cycloalkylaryl, and an aryl groupthat is mono- or di-substituted with C₁-C₁₂ alkyl or C₁-C₁₂ alkoxy; (4)C₁-C₆ alkyl, C₃-C₆ cycloalkyl, C₃-C₅ cycloalkyloxy(C₁-C₆)alkyl,aryl(C₁-C₆)alkyl, aryloxy(C₁-C₆)alkyl, mono- ordi-(C₁-C₆)alkylaryl(C₁-C₆)alkyl, mono- ordi-(C₁-C₆)alkoxyaryl(C₁-C₆)alkyl, haloalkyl, andmono(C₁-C₆)alkoxy(C₁-C₆)alkyl; (5) C₁-C₆ alkoxy, C₃-C₅ cycloalkoxy,cycloalkyloxy(C₁-C₆)alkoxy, aryl(C₁-C₆)alkoxy, aryloxy(C₁-C₆)alkoxy,mono- or di-(C₁-C₆)alkylaryl(C₁-C₆)alkoxy, and mono- ordi-(C₁-C₆)alkoxyaryl(C₁-C₆)alkoxy; (6) aminocarbonyl,aminocarbonyl(C₁-C₁₈)alkylene, amino, mono- or di-alkylamino,diarylamino, piperazino, N—(C₁-C₁₈)alkylpiperazino, N-arylpiperazino,aziridino, indolino, piperidino, morpholino, thiomorpholino,tetrahydroquinolino, tetrahydroisoquinolino, pyrrolidyl, hydroxy,acryloxy, methacryloxy, and halogen; (7) —OX₇ or —N(X₇)₂, and (8) anunsubstituted or mono-substituted group chosen from pyrazolyl,imidazolyl, pyrazolinyl, imidazolinyl, pyrrolidinyl, phenothiazinyl,phenoxazinyl, phenazinyl, or acridinyl, wherein each substituent isindependently chosen from lengthening agent L, C₁-C₃ alkyl, C₁-C₃alkoxy, phenyl, hydroxy, amino or halogen; (D) R³ and R⁴ are eachindependently selected from hydrogen, C₁-C₈ alkyl, C₁-C₈ haloalkyl, andC₃-C₇ cycloalkyl, or R³ and R⁴ together form a spiro substituentselected from a substituted or unsubstituted spiro-carbocyclic ringcontaining 3 to 6 carbon atoms; and (E) R⁵ is selected from hydrogen and—C(O)—R¹³.
 5. The indeno-fused ring compound of claim 4, wherein saidindeno-fused ring compound is represented by the following Formula Ia,

wherein t is selected from 0 to
 4. 6. The indeno-fused ring compound ofclaim 5, wherein Q′ is selected from —CN, —C(O)OR^(a), —C(O)R^(a),—C≡C—R^(a), —C(R^(a))═C(R^(a))(R^(a)), —OC(O)R^(a), —OC(O)OR^(a),—SR^(a), —OS(O₂)R^(b) and —C(O)NR^(a)R^(a).